Manfred Schlosser

Site selective functionalizations of fluorinated heterocycles (2006)

A review. Fluorine remains an insiders' tip in the life sciences as it enables the fine-tuning of biol. properties. However, the synthesis of fluorine-substituted target compds. is not always...

The "off-shore" construction of optionally substituted 4-trifluoromethyl-2-quinolinones (2006)

Heterocyclic chem. continues to be in the focus of life science-oriented research. Fluorine, a unique tool for finetuning biol. properties, offers an extra bonus in this context. The lecture features...

Leroux, Frederic, Lefebvre, Olivier, Schlosser, Manfred

Treatment of ortho-lithiated tert-Bu N-arylcarbamates (i.e., BOC-protected anilines) with N-(trifluoroacetyl)piperidine provides 2-(N-BOC-amino)aryl trifluoromethyl ketones which, upon reaction with...

In search of simplicity and flexibility: a rational access to twelve fluoroindolecarboxylic acids (2006)

Schlosser, Manfred, Ginanneschi, Assunta, Leroux, Frederic

All twelve indolecarboxylic acids carrying both a fluorine substituent and a carboxy group at the benzo ring have been prepd. either directly from the corresponding fluoroindoles or from the...

Metalated 1-(p-methoxybenzyl)pyrazole: a structural chameleon (2006)

Ondi, Levente, Schlosser, Manfred

When treated with either butyllithium or lithium diisopropylamide, 1-(p-methoxybenzyl)pyrazole undergoes metalation at the exocyclic alpha-position but mutates to the 5-lithio species in the course...

Metal-bearing and trifluoromethyl-substituted pyrimidines: generation and functionalization (2006)

Schlosser, Manfred, Lefebvre, Olivier, Ondi, Levente

5-Pyrimidyllithium species are fairly stable when the metal is flanked by two electron-withdrawing substituents such as trifluoromethyl and chlorine or bromine. Thus, the corresponding 5-carboxylic...

Fluorine-flanked congested sites: Minimal, though perceptible buttressing effects on the proton mobility of arenes (2005)

Heiss, Christophe, Leroux, Frederic, Schlosser, Manfred

(2,6-Difluorophenyl)trimethylsilane, -triethylsilane and -triisopropylsilane undergo sec-butyllithium-mediated metalation at the 3- and 4-position (ortho and meta relative to the halogen) in ratios...

Meta- rather than ortho-directed metalations: Buttressing effects prejudicing the proton abstraction from (2,6-dihalophenyl)silanes (2005)

Heiss, Christophe, Cottet, Fabrice, Schlosser, Manfred

(2,6-Dichlorophenyl)trimethyl- and -triethylsilane exhibit untypical reactivity patterns toward strong bases. When treated at -100 DegC with lithium 2,2,6,6-tetramethylpiperidide, they give rise to...

The abnormal behavior of an atropisomer: 3,3'-dibromo-1,1'-difluoro-2,2'-binaphthyl reacting with alkyllithium compounds (2005)

Leroux, Frederic, Mangano, Giuseppe, Schlosser, Manfred

1-Fluoro-2-(triethylsilyl)naphthalene and other 1-fluoronaphthalene derivs. bearing a metalation-resistant substituent at the 2-position proved to be totally inert toward base attack....

Fluoronaphthalene building blocks via arynes: A solution to the problem of positional selectivity (2005)

Masson, Eric, Schlosser, Manfred

When 3-fluoro- and 3-chloro-1,2-didehydrobenzenes are generated in the presence of 2-(trimethylsilyl)furan, two regioisomeric cycloadducts are formed in a 1:2 ratio. However, regioselectivity can be...

Metalation and derivatization of all six dichlorobenzotrifluorides: Site selectivities (2005)

Masson, Eric, Marzi, Elena, Cottet, Fabrice, Bobbio, Carla, Schlosser, Manfred

The metalation of 2,3-, 2,6-, 2,4- and 3,5-dichlorobenzotrifluorides can be readily effected with std. reagents such as lithium diisopropylamide, lithium 2,2,6,6-tetramethylpiperidide, and...

The structural proliferation of fluorinated building blocks by regiochemically exhaustive functionalizations (2005)

The reactivity of 2-fluoro- and 2-chloropyridines toward sodium ethoxide: Factors governing the rates of nucleophilic (het)aromatic substitutions (2005)

Organofluorine compds. do not grow on trees. They have to be prepd. by introducing the halogen into the carbon backbone at a suitable stage of the synthesis sequence. From a logistic point of view,...

Schlosser, Manfred, Rausis, Thierry

The relative displacement rates of the halide substituent from 2-fluoro- and 2-chloropyridines by EtONa in EtOH at +25 Deg were assessed by competition kinetics. The 2-fluoropyridine reacts 320 times...

The kinetic acidity of oligofluorobenzenes correlated with their gas phase deprotonation energies (2005)

Schlosser, Manfred, Marzi, Elena

The relative reactivities of fluorobenzene, all di-, tri-, and tetrafluorobenzenes and pentafluorobenzene toward sec-butyllithium have been assessed in THF at -100 DegC. At this temp. no subsequent...

Converting core compounds into building blocks: The concept of regiochemically exhaustive functionalization (2005)

Marzi, Elena, Bobbio, Carla, Cottet, Fabrice, Schlosser, Manfred

In a model study, 3-fluorophenol and 3-fluoropyridine were converted into all possible regioisomers of the corresponding carboxylic acids by passing through the corresponding organometallic...

A large-scale low-cost access to the lithium 2,2,6,6-tetramethylpiperidide precursor (2005)

Kampmann, Detlef, Stuhlmueller, Georg, Simon, Roger, Cottet, Fabrice, Leroux, Frederic, Schlosser, Manfred

Wolff-Kishner-Huang redn. of the cheap 2,2,6,6-tetramethyl-4-piperidinone provides the expensive 2,2,6,6-tetramethylpiperidine, the precursor to lithium 2,2,6,6-tetramethylpiperidide, in high yield....

The metalation of 1- and 2-(trifluoromethyl)naphthalenes: Noteworthy site selectivities (2005)

Cottet, Fabrice, Castagnetti, Eva, Schlosser, Manfred

This article provides insight into the various factors by which electroneg. substituents affect the kinetic acidity of arenes and, more specifically, naphthalenes. Both 1- and...

Heterosubstituted or functionalized derivatives of 1- and 2-(trifluoromethyl)naphthalenes emanating from aryne adducts (2005)

Bailly, Frederic, Cottet, Fabrice, Schlosser, Manfred

More than two dozen new CF3-substituted naphthalene derivs. were prepd. in an expedient way by employing 3- and 4-(trifluoromethyl)benzyne as the key intermediates. 2- And 4-Chlorobenzotrifluoride...

pi-Arene/Metal Binding: An Issue Not Only of Structure but Also of Reactivity (2005)

Masson, Eric, Schlosser, Manfred

A trimethyl-, triethyl-, or triisopropylsilyl group attached to the meta position of toluene retards the rate of permutational H/metal interconversion with butyllithium in the presence of K...

Promoting or preventing haloaryllithium isomerizations: differential basicities and solvent effects as the crucial variables (2005)

Heiss, Christophe, Rausis, Thierry, Schlosser, Manfred

Deprotonation-triggered heavy halogen migrations should become a favorite tool in arene synthesis if their occurrence and outcome could be made predictable. Particularly attractive, though extremely...

Selective Functionalization of 2-Fluoropyridine, 2,3-Difluoropyridine, and 2,5-Difluoropyridine at Each Vacant Position (2005)

Bobbio, Carla, Schlosser, Manfred

The concept of "regioexhaustive substitution" has been successfully applied to 2-fluoro-, 2,3-difluoro-, and 2,5-difluoropyridine. All vacant positions were amenable to regioselective metalation and...

Removal of fluorine from and introduction of fluorine into polyhalopyridines: an exercise in nucleophilic hetarenic substitution (2005)

Bobbio, Carla, Rausis, Thierry, Schlosser, Manfred

Starting from six industrially available fluorinated pyridines, an expedient access to all three tetrafluoropyridines, all six trifluoropyridines, and the five non-com. difluoropyridines was...

The site-selective functionalization of halogen-bearing phenols: an exercise in diversity-oriented organometallic synthesis (2005)

Marzi, Elena, Schlosser, Manfred

The organometallic approach to diversity-oriented org. synthesis was subjected to a further test, this time in the phenol series. The model compds. selected were 2,3,6-trifluorophenol, the three...

The gas phase acidity of oligofluorobenzenes and oligochlorobenzenes: about the additivity or non-additivity of substituent effects (2005)

Hyla-Kryspin, Isabella, Grimme, Stefan, Bueker, Heinz H., Nibbering, Nico M. M., Cottet, Fabrice, Schlosser, Manfred

The deprotonation energies of benzene, fluorobenzene, all di-, tri-, and tetrafluorobenzenes, pentafluorobenzene, chlorobenzene, all di-, tri-, and tetrachlorobenzenes, and pentachlorobenzene have...

Regiochemically flexible substitutions of di-, tri-, and tetrahalopyridines: the trialkylsilyl trick (2005)

Schlosser, Manfred, Bobbio, Carla, Rausis, Thierry

2,4-Difluoropyridine, 2,4-dichloropyridine, 2,4,6-trifluoropyridine, 2,4,6-trichloropyridine and 2,3,4,6-tetrafluoropyridine react with std. nucleophiles exclusively at the 4-position under halogen...

The 2 * 3 toolbox of organometallic methods for regiochemically exhaustive functionalization (2005)

Metalation/functionalization sequences applied to 2-bromo-3-fluoroquinolines (2005)

A review. This review describes a concept aimed at rational and maximal structure proliferation. To this end, simple arom. or heterocyclic starting materials, often bulk chems., are converted into...

Ondi, Levente, Volle, Jean-Noel, Schlosser, Manfred

Mono- and disubstituted 2-bromo-3-fluoroquinolines are readily accessible. They can be converted into the 3-fluoroquinoline-2-carboxylic acids by consecutive halogen/metal permutation and into the...

Rerouting Nucleophilic Substitution from the 4-Position to the 2- or 6-Position of 2,4-Dihalopyridines and 2,4,6-Trihalopyridines: The Solution to a Long-Standing Problem (2005)

Schlosser, Manfred, Rausis, Thierry, Bobbio, Carla

2,4-Difluoro-, 2,4,6-trifluoro-, and 2,3,4,6-tetra(fluoro)pyridine undergo nucleophilic substitution preferentially if not exclusively at the 4-position. However, after the introduction of a...

Alpha-fluorinated ethers, thioethers, and amines: anomerically biased species (2005)

Leroux, Frederic, Jeschke, Peter, Schlosser, Manfred

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Regioexhaustive Functionalizations: To Miss an Isomer Means to Miss a Chance (2005)

The preparation of organolithium reagents and intermediates (2004)

Leroux, Frederic, Schlosser, Manfred, Zohar, Elinor, Marek, Ilan

A review. Only the most important methods for the generation of organometallic reagents and intermediates are covered in this review. This holds for the reductive insertion of Li into org. halides,...

Logistic flexibility in the preparation of isomeric halopyridinecarboxylic acids (2004)

Cottet, Fabrice, Schlosser, Manfred

Although there are many conceivable ways to functionalize, and specifically carboxylate, 2-chloro-4-(trifluoromethyl)pyridine optionally at all three vacant positions, it is more straightforward to...

Brominated 4-(trifluoromethyl)pyrimidines: A convenient access to versatile intermediates. [Erratum to document cited in CA141:395506] (2004)

Ondi, Levente, Lefebvre, Olivier, Schlosser, Manfred

Throughout the paper, the incorrect reagent names "phosphorus tribromide\" and "phosphorus trichloride" should be replaced by the correct names "phosphoric tribromide" (POBr3) and "phosphoric...

Buttressing Effects on Haloarene Deprotonation: A Merely Kinetic or Also Thermodynamic Phenomenon? (2004)

Gorecka, Joanna, Heiss, Christophe, Scopelliti, Rosario, Schlosser, Manfred

(2,6-Dichlorophenyl)- and (2,6-dibromophenyl)trialkylsilanes undergo hydrogen/metal interconversion preferentially at the 4- rather than 3-position. However, the organometallic species generated by...

Three chloro(trifluoromethyl)pyridines as model substrates for regioexhaustive functionalization (2004)

Cottet, Fabrice, Schlosser, Manfred

As a further test of the concept of regioexhaustive functionalization, 2-chloro-6-(trifluoromethyl)pyridine, 2-chloro-5-(trifluoromethyl)pyridine and 3-chloro-4-(trifluoromethyl)pyridine were each...

Brominated 4-(trifluoromethyl)pyrimidines: A convenient access to versatile intermediates (2004)

Ondi, Levente, Lefebvre, Olivier, Schlosser, Manfred

An expedient route to all three monobrominated and all three dibrominated isomers of 4-(trifluoromethyl)pyrimidine, and to several other halogenated pyrimidines, is described. Key steps are the...

b,b-Difluoro analogs of a-oxo-b-phenylpropionic acid and phenylalanine (2004)

Schlosser, Manfred, Brugger, Nadia, Schmidt, Werner, Amrhein, Nikolaus

A simple three-step procedure converted the readily accessible (2-bromo-1,1-difluoroethyl)arenes into a-aryl-a,a-difluoroacetaldehydes. Subsequent hydrocyanation, hydrolysis, oxidn. and again...

Further metalations and functionalizations of chloro-, bromo- and iodo(trifluoromethyl)pyridines (2004)

Cottet, Fabrice, Marull, Marc, Mongin, Florence, Espinosa, David, Schlosser, Manfred

In accordance with the concept of regioexhaustive functionalization, both 3-chloro-2-(trifluoromethyl)pyridine and 2-bromo-6-(trifluoromethyl)pyridine were converted each time into the three possible...

The regioexhaustive functionalization of difluorophenols and trifluorophenols through organometallic intermediates (2004)

Marzi, Elena, Gorecka, Joanna, Schlosser, Manfred

2,4-Difluorophenol, 2,5-difluorophenol, 2,3-difluorophenol, 3,5-difluorophenol, 3,4-difluorophenol, 2,4,5-trifluorophenol and 2,3,4-trifluorophenol were converted into all 18 possible di- or...

The structural proliferation of 2,6-difluoropyridine through organometallic intermediates (2004)

Schlosser, Manfred, Rausis, Thierry

Contrary to a literature claim, 2,6-difluoropyridine-3-carboxaldehyde can be readily prepd. by consecutive treatment of 2,6-difluoropyridine with lithium diisopropylamide and N,N-dimethylformamide....

The superbase-mediated pairwise substitution of the 2,2'- and 6,6'-positions in a biphenyl derivative (2004)

Schlosser, Manfred, Mangano, Guiseppe, Leroux, Frederic

The superbasic mixt. of butyllithium and potassium tert-butoxide is powerful enough to enable the double proton abstraction from one ortho and one ortho' position of 4,4'-di-tert-butylbiphenyl. In...

Regioflexibility in the functionalization of multiply halogenated quinolines (2004)

Marull, Marc, Schlosser, Manfred

4-Bromo-6-fluoro-2-(trifluoromethyl)quinoline and 4-bromo-7-fluoro-2-(trifluoromethyl)quinoline were selected as model substrates to explore under what conditions regiochem. exhaustive...

Atropisomeric biarylbisphosphines derived from 2,2-difluoro-1,3-benzodioxole (2004)

Leroux, Frederic, Gorecka, Joanna, Schlosser, Manfred

Starting from the inexpensive 2,2-difluoro-1,3-benzodioxole or its 5-bromo deriv., two new atropisomeric bisphosphines have been prepd. which, after racemate resoln., exhibit attractive features as...

Deprotonation-triggered heavy-halogen migrations as a key to the structural elaboration of 2,2-difluoro-1,3-benzodioxole (2004)

Gorecka, Joanna, Leroux, Frederic, Schlosser, Manfred

Bromine migration in lithiated 4-bromo-2,2-difluoro-1,3-benzodioxoles was achieved by protecting the 7-position of the bicycle by trialkylsilyl group, thus giving access to...

An improved access to 4-trifluoromethyl-2(1H)-quinolinones: The "watering protocol" (2004)

Marull, Marc, Lefebvre, Olivier, Schlosser, Manfred

Condensation of anilines with Et 4,4,4-trifluoroacetoacetate to afford the corresponding 4,4,4-trifluoro-3-oxobutaneanilides, precursors to 4-(trifluoromethyl)-2-quinolinones, can be favored and the...

Buttressing effects rerouting the deprotonation and functionalization of 1,3-dichloro- and 1,3-dibromobenzene (2003)

Heiss, Christophe, Marzi, Elena, Schlosser, Manfred

A systematic comparison between 1,3-difluorobenzene, 1,3-dichlorobenzene, and 1,3-dibromobenzene did not reveal major differences in their behavior towards strong bases such as lithium...

Exploring structural opportunities: The regioflexible substitution of 1,3-difluorobenzene (2003)

Schlosser, Manfred, Heiss, Christophe

To demonstrate the superiority of modern organometallic methods, the inexpensive starting material 1,3-difluorobenzene has been selectively converted into the three benzoic acids and all seven...

The 2 x 3 toolbox of organometallic methods for regiochemically exhaustive functionalization of aromatic and heterocyclic substrates (2003)

4-(trifluoromethyl)quinoline derivatives (2003)

There are not so many fluorine, trifluoromethyl and trifluoromethoxy contg. arenes and heterocycles that are com. available and inexpensive. To exploit this bonanza optimally, one should be able to...

Lefebvre, Olivier, Marull, Marc, Schlosser, Manfred

Under carefully controlled conditions, Et 4,4,4-trifluoroacetoacetate (Et 4,4,4-trifluoro-3-oxobutanoate) can be condensed with anilines and subsequently cyclized to give...

Trifluoromethoxy Substituted Anilines: Metalation as the Key Step for Structural Elaboration (2003)

Leroux, Frederic, Castagnetti, Eva, Schlosser, Manfred

Trifluoromethoxy-substituted anilines undergo hydrogen/lithium permutation (\"metalation\") with optional site selectivity depending on the N-protective group employed. N-tert-Butoxycarbonyl-2- and...

Selective and efficient structural elaboration of 2-(trifluoromethyl)quinolinones (2003)

Marull, Marc, Schlosser, Manfred

The acid-catalyzed cyclization-condensation between anilines and Et 4,4,4-trifluoroacetoacetate affords 1,4-dihydro-2-trifluoromethyl-4H-4-quinolinones, which can easily be converted into...

The direct metalation and subsequent functionalization of trifluoromethyl-substituted pyridines and quinolines (2003)

Schlosser, Manfred, Marull, Marc

Depending on the choice of the reagent, 2-(trifluoromethyl)pyridine can be selectively metalated and subsequently carboxylated or otherwise functionalized either at the 3- or at the 6-position....

Recommendable routes to trifluoromethyl-substituted pyridine- and quinolinecarboxylic acids (2003)

Cottet, Fabrice, Marull, Marc, Lefebvre, Olivier, Schlosser, Manfred

As part of a case study, rational strategies for the prepn. of all ten 2-, 3-, or 4-pyridinecarboxylic acids and all nine 2-, 3-, 4-, or 8-quinolinecarboxylic acids bearing trifluoromethyl...

A homologous series of O- and N-functionalized 2,2-difluoro-1,3-benzodioxoles:; An exercise in organometallic methodology (2003)

Schlosser, Manfred, Gorecka, Joanna, Castagnetti, Eva

The conversion of 2,2-difluoro-1,3-benzodioxole, an exceptionally acidic arene, via a 4-lithiated intermediate into more than three dozen new derivs. was conceived as a case study. The lithiated...

Organometallic control over the regiospecificity of functionalization reactions: 1,2,3-trifluorobenzene and bromo derivatives thereof as substrates (2003)

Heiss, Christophe, Schlosser, Manfred

In a case study, 1,2,3-trifluorobenzene was functionalized at each of the two vacant positions [producing the benzoic acids HO2CC6H2F3-2,3,4 F(I) and HO2CC6H2F3-3,4,5 (I)] and, in addn., bromine was...

Sequestered alkyllithiums: why phenyllithium alone is suitable for betaine-ylide generation (2003)

Wang, Qian, Deredas, Dariusz, Huynh, Cyril, Schlosser, Manfred

The key step in the trans-selective modification of the Wittig reaction is the a-lithiation of the lithium bromide coordinated ylide-aldehyde adduct (the so-called \"P-betaine\"). The olefination...

Silyl-mediated halogen/halogen displacement in pyridines and other heterocycles (2002)

Schlosser, Manfred, Cottet, Fabrice

Heating with bromotrimethylsilane converts 2-chloropyridine into 2-bromopyridine and 2-chloro-6-methylpyridine into 2-bromo-6-methylpyridine. Both 2-chloropyridines and 2-bromopyridines give the...

Creating structural manifolds from a common precursor: basicity gradient-driven isomerization of halopyridines (2002)

Schlosser, Manfred, Bobbio, Carla

5-Chloro-2,3-difluoropyridine, an intermediate in the manufg. process of an industrial pesticide, can be hydrolyzed to 5-chloro-3-fluoro-2H-pyridinone and the latter converted into...

The "aryne" route to biaryls featuring uncommon substituent patterns (2002)

Leroux, Frederic, Schlosser, Manfred

The reaction of 1-bromo-3-halo-2-iodobenzene (I; X = Cl) with butyllithium gives 62% (II; X = Cl) similarly reaction of [I; X = F(III)] gave 64% II (X = F). These reactions involve the immediate...

A simple method for the displacement of bromine by fluorine at tertiary, benzylic or non-classical secondary sites (2002)

Leroux, Frederic, Garamszegi, Laszlo, Schlosser, Manfred

Using in situ generated iodine fluoride as the reagent, bromine can be replaced by fluorine at carbocation-sustaining sites. Iodine fluoride or, being its operational equiv., the mixt. of...

The basicity gradient-driven migration of iodine: conferring regioflexibility on the substitution of fluoroarenes (2002)

Rausis, Thierry, Schlosser, Manfred

Six different fluoroarenes were submitted to the same transformations. Direct deprotonation with alkyllithium or lithium dialkylamide as reagents and subsequent carboxylation afforded acids. These...

Switchable reactivity: the site-selective functionalization of trifluoromethyl-substituted pyrazoles (2002)

Schlosser, Manfred, Volle, Jean-Noel, Leroux, Frederic, Schenk, Kurt

Modern organometallic methods enable the regioflexible conversion of simple heterocyclic starting materials into families of isomers and congeners. Depending on the choice of the reagent,...

Fluoro- or trifluoromethyl-substituted benzyl and phenethyl alcohols: Substrates for metal-mediated site-selective functionalization (2002)

Marzi, Elena, Spitaleri, Andrea, Mongin, Florence, Schlosser, Manfred

It was possible to functionalize the three fluorobenzyl alcs. and the three 2-(fluorophenyl)ethanols by metalation and subsequent carboxylation, the prototype electrophilic trapping reaction....

1-Ethoxy-3-trifluoromethyl-1,3-butadiene and congeners as Diels-Alder components opening an entry to functionalized (trifluoromethyl)benzenes and -pyridines (2002)

Volle, Jean-Noel, Schlosser, Manfred

1-Ethoxy-3-trifluoromethyl-1,3-butadiene and its 2-bromo- and 2-phenyl-substituted derivs. have been prepd. by Wittig methylenation of the corresponding 4-ethoxy-1,1,1-trifluoro-3-buten-2-ones, which...

The trifluoromethoxy group:- a long-range electron-withdrawing substituent (2002)

Castagnetti, Eva, Schlosser, Manfred

Judged by its capacity to promote a hydrogen/metal permutation at an ortho position, the trifluoromethoxy group is superior to both the methoxy and trifluoromethyl groups. Moreover, like CF3 and...

Trifluoromethyl-substituted pyridines through displacement of iodine by in situ generated (trifluoromethyl)copper (2002)

Cottet, Fabrice, Schlosser, Manfred

A literature method reported for the prepn. of trifluoromethyl substituted benzenes from iodobenzene and congeners was successfully extended to the pyridine series. 2-Iodopyridines can be converted...

Organometallics in Synthesis: A Manual, 2nd edition (2002)

Regiochemical flexibility: the optional functionalization of 2,3,5-trihalopyridines at the 4- or 6-position (2001)

Bobbio, Carla, Schlosser, Manfred

A deprotonation study was performed using 2,3,5-trichloropyridine, 3,5-dichloro-2-fluoropyridine, and 5-chloro-2,3-difluoropyridine as the substrates. Upon reaction with lithium diisopropylamide...

1,2-Didehydro-3- and -4-(trifluoromethoxy)benzene: the \"aryne\" route to 1- and 2-(trifluoromethoxy)naphthalenes (2001)

Schlosser, Manfred, Castagnetti, E.

Upon treatment of 1-bromo-2-(trifluoromethoxy)benzene with lithium diisopropylamide (LDA) at -100 DegC, 3-bromo-2-(trifluoromethoxy)phenyllithium is generated. It can be trapped as such, but...

Dimetalation: the acidity of monometalated arenes towards superbasic reagents (2001)

Baston, Eckhard, Maggi, Raimondo, Friedrich, Kirstin, Schlosser, Manfred

Twofold H/metal interconversions (dimetalations) can be accomplished with spiny arenes (tert-butylbenzene, 1,4-di-tert-butylbenzene, 1,1,3,3-tetramethylindane and congeners) and N,N-crowded anilines...

The organometallic approach to molecular diversity - halogens as helpers (2001)

The organoalkali route to vitamin A and b-carotene (2001)

A review. Strategies to functionalize simple, though structurally challenging, compds. in regiodivergent manner are outlined. The starting materials are inexpensive (5-500 e/mol) arenes or...

Rauchschwalbe, Gunter, Zellner, Armin, Schlosser, Manfred

The reductive cleavage of Me vinyl-b-ionyl ether or the deprotonation of 3,2',6',6'-tetramethyl-5-(1-cyclohexenyl)-1,3-pentadiene gives rise to an organometallic C15 species that combines selectively...

Pentadienyl type lithium and potassium species: the regioselectivity of their reactions with electrophiles (2001)

Schlosser, Manfred, Zellner, Armin, Leroux, Frederic

Seven structurally distinct pentadienyl type lithium and potassium compds. were screened against a variety of electrophiles in order to assess the regioselectivity of the trapping reactions....

The acidity of chloro-substituted benzenes: a comparison of gas phase, Ab initio, and kinetic data (2001)

Schlosser, Manfred, Marzi, Elena, Cottet, Fabrice, Buker, Heinz H., Nibbering, Nico M. M.

The deprotonation energies of benzene, chlorobenzene, all di-, tri-, tetrachlorobenzenes, and pentachlorobenzene have been detd. in the gas phase using a Fourier transform ion cyclotron resonance...

Fluorophenols and (trifluoromethyl)phenols as substrates of site-selective metalation reactions: to protect or not to protect (2001)

Marzi, Elena, Mongin, Florence, Spitaleri, Andrea, Schlosser, Manfred

O-Methoxymethyl (MOM) protected fluorophenols can be cleanly metalated and subsequently be submitted to site-selective electrophilic substitution. The 2- and 4-isomers exhibit ambivalent reactivity:...

Extensive halogen scrambling and buttressing effects encountered upon treatment of oligobromoarenes with bases (2001)

Mongin, Florence, Marzi, Elena, Schlosser, Manfred

As a rule, tri-, tetra- and pentahaloarenes readily undergo ortho-lithiation when treated with amide-type bases. However, halogen migration occurs whenever the substrate contains three or more...

Pentadienyltitaniums as versatile intermediates: regio- and stereo-selectivities (2001)

Zellner, Armin, Schlosser, Manfred

The adduct obtained upon consecutive treatment of 1,4-dienes with butyllithium in the presence of potassium tert-butoxide, chlorotri(isopropyloxy)titanium and a carbonyl compd. contains the...

Strategies for the selective functionalization of dichloropyridines at various sites (2001)

Marzi, Elena, Bigi, Anna, Schlosser, Manfred

Whereas 2,3-dichloropyridine and 2,5-dichloro-4-(lithiooxy)pyridine undergo deprotonation exclusively at the 4- and 2-positions, resp., optional site selectivity can be implemented with 2,5- and...

2-, 3-, and 4-(trifluoromethoxy)phenyllithiums: versatile intermediates offering access to a variety of new organofluorine compounds (2001)

Castagnetti, Eva, Schlosser, Manfred

Consecutive treatment of (trifluoromethoxy)benzene with sec-butyllithium and electrophilic reagents affords previously inaccessible ortho-substituted derivs. in generally excellent yields....

Odor-structure relationships using fluorine as a probe (2000)

Michel, Dominique, Schlosser, Manfred

Eight ethers, nine esters and one ketone were submitted to a systematic structural variation by replacing a hydrogen atom in the vicinity of the oxo function by fluorine and Me. As long as steric...

Enhancement of benzylic basicity by a fluorine substituent at the para-position: a case of lone pair/lone pair repulsion (2000)

Faigl, Ferenc, Marzi, Elena, Schlosser, Manfred

The introduction of a halogen atom at any arom. position of toluene considerably accelerates the base-promoted deprotonation of the Me group. P-Fluorotoluene is the only exception; proton abstraction...

Fluorine-sacrificial cyclizations as an access to 5-fluoropyrazoles (2000)

Volle, Jean-Noel, Schlosser, Manfred

Me 3-methoxy-2-trifluoromethylacrylate, readily prepd. by Wittig reaction from Me 3,3,3-trifluoropyruvate, has been treated with a no. of aryl(or heteroaryl)hydrazines. Under mild base catalysis, the...

Bridging the final gap in stereocontrolled Wittig reactions: methoxymethoxy-armed allylic phosphorus ylides affording conjugated dienes with high cis selectivity (2000)

Wang, Qian, El Khoury, Mirella, Schlosser, Manfred

After treatment with an appropriate base (butyllithium or sodium amide), 2-alkenyltris(2-methoxymethoxyphenyl)phosphonium salts carrying an allyl, crotyl, or prenyl (3-methyl-2-butenyl) side chain...

The rate retarding effect of alkyl groups on arene metalation quantified (2000)

Baston, Eckhard, Wang, Qian, Schlosser, Manfred

Metalation/trapping sequences applied to relatively inert, tert-alkyl substituted arenes tend to give poor yields unless the reagent is used in high concns. Under optimized conditions, even...

Rate enhancing and rate retarding effects of methoxy substituents on arene metalation (1999)

Maggi, Raimondo, Schlosser, Manfred

Competition expts. have been performed to det. the rates, relative to benzene, with which anisole, the three dimethoxybenzenes and the three trimethoxybenzenes are deprotonated by sec-butyllithium....

The simultaneous in-situ generation of aldehydes and phosphorus ylides. A convenient multi-step one-pot olefination protocol (1999)

Wang, Qian, Wei, Heng-Xu, Schlosser, Manfred

Li a-(dimethylamino)alkoxides resulting from the nucleophilic addn. of an organolithium reagent to DMF are basic enough to deprotonate alkyltriphenylphosphonium salts suspended in THF. The aldehydes,...

Isopulegol as a model compound. Metalation and substitution of an allylic position in the presence of an unprotected hydroxy function (1999)

Schlosser, Manfred, Kotthaus, Martina

When treated with BuLi and KOCMe3 for 2 h at 0 Deg in hexane, the unsatd. monoterpenic alc. isopulegol is simultaneously deprotonated at the hydroxy function and the allylic Me group. The metaloxy...

The Chemical and Physiological Size of Fluorine (1999)

An unprecedented elimination-driven migration: the reductive dihalobornane-camphene rearrangement (1998)

The effect of fluorine as a substituent on reactions and biol. activity of natural products was reviewed with 324 refs.

Garamszegi, Laszlo, Schlosser, Manfred

In the rearrangement of exo-2,10-dibromobornane to camphene it was demonstrated that even complex elimination processes which involve the breaking and making of several bonds can be brought about in...

Fluorinated analogs of retinoids. Stereocontrolled synthesis employing fluoroisoprenoidal Horner ylides (1998)

Wei, Heng-Xu, Schlosser, Manfred

An improved method for the prepn. of Me2C:CFCO2Et is described. The two stereoisomers (E)- and (Z)-BrCH2CMe:CFCO2Et obtained by g-bromination are sepd. and can be individually converted into the...

The super base approach to flurbiprofen: an exercise in optionally site-selective metalation (1998)

Schlosser, Manfred, Geneste, Herve

A superior route to the analgesic flurbiprofen has been devised. Key steps are the selective deprotonation of 3-fluorotoluene with tert-butyllithium in the presence of potassium tert-butoxide...

a-Deprotonated allyl ethers: conformational mobility and conformational preferences (1998)

Margot, Christian, Maccaroni, Paola, Leroux, Frederic, Schlosser, Manfred

Tert-BuLi is best suited to accomplish an H-metal exchange at the a-position of g-alkyl branched allyl ethers. Rapid torsional equilibration occurs at the g-terminus of the deprotonated allyl unit,...

A novel aldol condensation alternative: a,b-unsaturated aldehydes from 3-hydroxy-1-alkynes via dihydrodioxepins (1998)

Wei, Heng-xu, Schlosser, Manfred

The controlled aldol condensation between an aliph. ketone and an acetaldehyde equiv. remains a challenge. One soln. to this evergreen problem consists of the nucleophilic addn. of acetylene to the...

Fluorine as an ally and a spy (1998)

The organometallic route to benzylamine type monoamine oxidase inhibitors (1998)

Fluorine, be it as individual atoms or CF3 groups, facilitates and orients the deprotonation of arenes and hetarenes (pyridines etc.). Representative examples will illustrate the concept of "optional...

Schlosser, Manfred, Geneste, Herve

N-Methyl-N-(2-propynyl)piperonylamine can be simultaneously lithiated at the terminal acetylenic and at that arom. position which is flanked by both the side chain and an oxygen atom. Under carefully...

Bis- and oligo(trifluoromethyl)benzenes: hydrogen/metal exchange rates and gas-phase acidities (1998)

Schlosser, Manfred, Mongin, F., Porwisiak, Jacek, Dmowski, Wojciech, Buker, Heinz H., Nibbering, Nico M. M.

The proton mobilities (kinetic acidities) of bis- and tris(trifluoromethyl)benzene are dictated to a large extent by steric factors; the trifluoromethyl group is a fairly bulky substituent that can...

Three complementary methods offering access to 5-substituted 1,2,3,4-tetrahydroisoquinolines (1998)

Schlosser, Manfred, Simig, Gyula, Geneste, Hervi

The scope and limitations of three independent, though related routes leading to 5-substituted tetrahydroisoquinolines are explored: the Pictet-Spengler type cyclization of ortho-substituted...

Switching on and off metalation sites in triarylphosphines by manipulating substrate coordination (1998)

Desponds, Olivier, Huynh, Cyril, Schlosser, Manfred

The inductive electron-withdrawing effect of the pos. charged P atom in triarylphosphine-BH3 adducts is largely compensated by the steric congestion caused in its vicinity. Therefore, Ph3P.BH3 reacts...

Parametrization of substituents: effects of fluorine and other heteroatoms on OH, NH, and CH acidities (1998)

Strained rings to assess the "endo preference" of 2-alkyl branched 2-alkenylpotassium species (1998)

Fluorine leaves nobody indifferent; it inflames emotion, be that affections or aversions. As a substituent it is rarely boring, always good for a surprise, but often completely unpredictable. It...

Kotthaus, Martina, Schlosser, Manfred

Upon deprotonation using trimethylsilylmethylpotassium or butyllithium in the presence of potassium tert-butoxide, two allylic organopotassium species are generated from the (E)-isomeric...

The regioselectivity of 1,3-disubstituted allylmetal species towards electrophiles. 1-(Trimethylsilyl)alk-2-enylpotassium compounds (1998)

Schlosser, Manfred, Franzini, Livia

1-(Trimethylsilyl)alk-2-enylpotassium species are readily generated by deprotonation of (alk-2-enyl)trimethylsilanes with the superbasic mixt. of BuLi and KOCMe3. Like the parent compd.,...

Halogen shuffling in pyridines: site selective electrophilic substitutions of 2-chloro-6-(trifluoromethyl)pyridine (1998)

Mongin, Florence, Tognini, Antonio, Cottet, Fabrice, Schlosser, Manfred

When treated with lithium diisopropylamide in THF at -85 Deg and subsequently with iodine, 2-chloro-6-(trifluoromethyl)pyridine is neatly converted into its 3-iodo deriv. The latter can be quant....

The effect of an alkoxy group on the kinetic and thermodynamic acidity of benzene and toluene (1998)

Schlosser, Manfred, Maccaroni, Paola, Marzi, Elena

2-, 3- And 4-Methoxytoluene can be selectively metalated at an O-adjacent ortho position when butylithium or tert-butyllithium in the presence of sodium (potassium) tert-butoxide or...

1,2,4-Tris(trifluoromethyl)benzene: selective lithiation and subsequent electrophilic substitution (1998)

Schlosser, Manfred, Porwisiak, Jacek, Mongin, Florence

1,2,4-Tris(trifluoromethyl)benzene quant. undergoes a hydrogen/metal exchange when treated with an ethereal soln. of lithium 2,2,6,6-tetramethylpiperidide. Proton abstraction occurs concomitantly...

How 2-anilinovinyl perfluoroalkyl ketones can be mechanistically correlated with their cyclization products 2-(perfluoroalkyl)quinolines (1997)

Schlosser, Manfred, Keller, Holger, Sumida, Shin-Ichi, Yang, Jin

When heated in the presence of phosphoryl chloride, 2-anilinovinyl perfluoroalkyl ketones [e.g., 4-anilino-1,1,1-trifluoro-3-buten-2-one] gave 2-(perfluoroalkyl)quinolines [e.g.,...

Additivity of substituent effects in the fluoroarene series: equilibrium acidity in the gas phase and deprotonation rates in ethereal solution (1997)

Buker, H. H., Nibbering, N. M. M., Espinosa, D., Mongin, F., Schlosser, Manfred

Benzene and all mono-, di-, tri, tetra-, and pentafluoro-substituted derivs. thereof were equilibrated with the corresponding aryl anions in the gas phase. Perfect additivity of the substituent...

Determination of 4-Hydroxy-2,5-dimethyl-3(2H)-furanone and 2(or 5)-Ethyl-4-hydroxy-5(or 2)-methyl-3(2H)-furanone in Pentose Sugar-Based Maillard Model Systems by Isotope Dilution Assays (1997)

Blank, Imre, Fay, Laurent B., Lakner, Frederick J., Schlosser, Manfred

The formation of 4-hydroxy-2,5-dimethyl-3(2H)-furanone (HDMF) and 2(or 5)-ethyl-4-hydroxy-5(or 2)-methyl-3(2H)-furanone (EHMF) from pentose sugars was studied in Maillard model systems. The amts....

No evidence for intramolecular hydrogen bonds in a-fluoro carboxamides (1997)

Michel, Dominique, Witschard, Martin, Schlosser, Manfred

RMeCFCONH2 (R = H, cyclohexyl, Ph, 4-ClC6H4, 2-pyridyl) are prepd. by treatment of the corresponding a-hydroxy carboxamides with Et2NSF3. IR spectra argue strongly against the existence of intramol....

Hydroxy- and carboxy-substituted allylsilanes. A simple and stereoselective method of preparation (1997)

Moret, Etienne, Franzini, Livia, Schlosser, Manfred

When treated with 2 equiv of a BuLi/KOCMe3 mixt., terminal olefins carrying unprotected OH or CO2H groups generate allylmetal intermediates which are trapped with Me3SiCl to afford functionalized...

The acidifying effects of chlorine and bromine: little difference (1997)

Mongin, Florence, Schlosser, Manfred

Lithium diisopropylamide deprotonates o- and p-bromochlorobenzene randomly at the two halogen adjacent positions. Obviously for steric reasons, the bulkier base lithium 2,2,6,6-tetramethylpiperidide...

A one-pot preparation of allylsilanes and (Z)-alk-2-enyl silanes (1997)

Desponds, Olivier, Franzini, Livia, Schlosser, Manfred

Metalation of 1-alkenes with a mixt. of BuLi and KOCMe3 in tetrahydropyran, followed by stereochem. equilibration and treatment with Me3SiCl, afforded (2-alkenyl)trimethylsilanes in good yield and...

2-Ethoxyvinyllithiums and diethoxyvinyllithiums: what makes them stable or fragile? (1997)

Schlosser, Manfred, Wei, Heng-xu

The elusive (E)-2-ethoxyvinyllithium can be readily generated in THF at -75 Deg from (E)-1-bromo-2-ethoxyethylene by halogen/metal exchange and subsequently trapped with electrophiles. Alkylation...

Conformational mobility and preferences of allyl-type organometallic intermediates. Dodec-2-enylpotassium (1997)

Franzini, Livia, Moret, Etienne, Schlosser, Manfred

Alk-2-enylpotassium compds. having endo conformation are synthetically very valuable precursors of (Z)-olefinic derivs. substituted at the outward allylic position. They may be generated by...

Halogen/metal vs. hydrogen/metal exchange. General or specific site selectivity as exemplified in the camphene series (1997)

Garamszegi, Laszlo, Schlosser, Manfred

(Z)-(3,3-dimethylbicyclo[2.2.1]hept-2-ylidene)methyllithium can be readily generated by treatment of (Z)-3-bromomethylene-2,2-dimethylbicyclo[2.2.1]heptane with Me3CLi. At -75 Deg, the organometallic...

2-Alkenylphosphonates and PO-ylides derived thereof in trans selective Horner-Wittig olefination reactions (1996)

Liu, Rong Qiang, Schlosser, Manfred

Allylic PO-ylides generated from dialkyl or diaryl 2-alkenylphosphonates by treatment with a strong base react with aldehydes to afford 1,3-dienes trans-selectively. The newly formed double bond...

2-Alkenyldiphenylphosphine oxides and PO-ylides derived thereof in trans selective Horner-Wittig olefination reactions (1996)

Liu, Rong Qiang, Schlosser, Manfred

Allylic PO-ylides generated by deprotonation of 2-alkenyldiphenylphosphine oxides with BuLi were used to prep. 1,3-dienes trans-selectively. The (Z/E) ratios of the newly formed double bond are 1:99...

About bases and superbases (1996)

Mongin, Florence, Maggi, Raimondo, Schlosser, Manfred

A review with 26 refs. on the authors work on metalation by bases and superbases. BuLi requires activation to become capable of abstracting a proton from weakly acidic hydrocarbons like...

A new generation of "instant ylides": powder mixtures of phosphonium salts and potassium hydride as storable precursors to Wittig reagents (1996)

El-Khoury, Mirella, Wang, Qian, Schlosser, Manfred

Mixing a finely pulverized alkyltriphenylphosphonium salt and potassium hydride in 1:1 molar ratio gives a ready-to-use powder the components of which react rapidly when tert-Bu Me ether is added...

Regioselective ortho-lithiation of chloro- and bromo-substituted fluoroarenes (1996)

Mongin, Florence, Schlosser, Manfred

Deprotonation of fluoroarenes carrying chlorine or bromine as addnl. substituents occurred always at a position adjacent to a fluorine if accomplished with potassium tert-butoxide activated...

(w - 1)-fluoroalk-(w - 1)-enoic acids. Potential fungicides (1996)

Michel, Dominique, Schlosser, Manfred

(w - 1)-Fluoroalk-(w - 1)-enoic acids of chain lengths C5-C15 were prepd. by consecutive bromofluorination and dehydrobromination of either alk-(w - 1)-enoic acids or alk-(w - 1)-enyl acetates, in...

Optional Site Selectivity in the Metalation of o- and p-Anisidine through Matching of Reagents with Neighboring Groups (1996)

Maggi, Raimondo, Schlosser, Manfred

N-Protected o- and p-anisidines (2- and 4-methoxyanilines) undergo a hydrogen/metal exchange at the position adjacent to either the oxygen or nitrogen atom depending on what organometallic base is...

a-Fluoro analogs of inflammation inhibiting a-arylpropionic acids (1996)

Schlosser, Manfred, Michel, Dominique, Guo, Zhi-wei, Sih, Charles J.

2-Aryl-2-fluoropropionic acids were prepd. by treatment of either Et a-hydroxycarboxylates or cyanohydrin O-silyl ethers with diethylaminosulfur trifluoride and subsequent hydrolysis. The Me ester of...

2,2-Di(ethoxy)vinyllithium: a synthetic equivalent of the ethyl acetate anion (1996)

Wei, Heng-xu, Schlosser, Manfred

2,2-Diethoxyvinyllithium (I) can be readily generated from 2-bromo-1,1-diethoxyethylene by treatment with butyllithium. Reaction of I with electrophiles e.g. chlorotrimethylsilane gives...

Reagent-modulated optional site selectivities: the metalation of o-, m- and p-halobenzotrifluorides (1996)

Mongin, Florence, Desponds, Olivier, Schlosser, Manfred

Chloro(trifluoromethyl)benzenes and bromo(trifluoromethyl)benzenes underwent deprotonation at a postion adjacent to the single halogen substituent when treated with alkyllithiums (at -75 DegC) and,...

2-(Trifluoromethyl)quinolines from anilines: a novel mode of isomerization and cyclization (1996)

Keller, Holger, Schlosser, Manfred

Deprotonation of N-ethylidene-tert-butylamine with lithium diisopropylamide and subsequent condensation with Et trifluoroacetate gives 4-tert-butylamino-1,1,1-trifluorobut-3-en-2-one. An exchange of...

Versatile 2-Fluoroacrylic Building Blocks for the Synthesis of Fluorinated Heterocyclic Compounds (1996)

Shi, Guo-qiang, Wang, Qian, Schlosser, Manfred

The Me ester of 2-fluoro-3-methoxyacrylic acid and the corresponding acyl chloride were used for the efficacious synthesis of fluorine-bearing pyrazolones, pyrimidines, coumarines and...

3-Fluoro-2-quinolones From Anilines (1996)

Maevers, Ursula, Berruex, France, Schlosser, Manfred

N-(Fluoro-3-methoxyacryloyl)anilines [2-fluoro-3-methoxy-2-propenanilides] can be prepd. by condensation between lithium anilides and Me 2-fluoro-3-methoxy-2-propenoate. For example, the reaction of...

1-Bromo-3,5-bis(trifluoromethyl)benzene: a versatile starting material for organometallic synthesis (1996)

Porwisiak, Jacek, Schlosser, Manfred

1-Bromo-3,5-bis(trifluoromethyl)benzene was selectively prepd. by treatment of 1,3-bis(fluoromethyl)benzene with N,N'-dibromo-5,5-dimethylhydantoin in strongly acidic media. A no. of synthetically...

2,2'-Bis(diphenylphosphino)biphenyl revisited (1996)

Desponds, Olivier, Schlosser, Manfred

The reaction between 2,2'-dilithiobiphenyl and two equiv. of chlorodiphenylphosphine is confirmed to afford equal amts. of 9-phenyl-9-phosphafluorene (2) and PPh3. 2,2'-Bis(diphenylphosphino)biphenyl...

About the "physiological size" of fluorine substituents: comparison of sensorially active compounds with fluorine and methyl substituted analogs (1996)

Schlosser, Manfred, Michel, Dominique

The taste of four fluoro substituted derivs. is almost indistinguishable from that of the parent compd. 4-(4-hydroxyphenyl)butan-2-one, the main flavor component of raspberries. The same holds for...

Sparteine-mediated a-lithiation of N-BOC-N-methylbenzylamine: Rapid racemization and subsequent deracemization (1995)

Schlosser, Manfred, Limat, Dominique

Upon a-lithiation of N-BOC-N-methylbenzylamine (tert-Bu N-benzyl-N-methylcarbamate) with sec-BuLi in the presence of (-)-sparteine, the pro-(S) proton is preferentially abstracted (kinetic resoln. of...

The Diels-Alder route to trifluoromethyl-substituted carbo- and heterocycles (1995)

Schlosser, Manfred, Keller, Holger

Starting with 1,1,1-trifluoroacetone, 3-(trifluoromethyl)-1-(trimethylsilyloxy)-1,3-butadiene has been prepd. as a mixt. of (Z) and (E) isomers. The diene undergoes [4 + 2] cycloaddn. reactions with...

O-Fluoromethyl carboxylates and O-fluoromethyl carbamates (1995)

Schlosser, Manfred, Limat, Dominique

The fluoride catalyzed reaction between acyl fluorides and monomeric formaldehyde affords fluoromethyl carboxylates in acceptable yields. Fluoromethyl fluoroformate, readily accessible from the...

The selective O-acylation of enolates providing simple entry to O-enesters (1995)

Limat, Dominique, Schlosser, Manfred

In the presence of catalytic amts. of a fluoride source, O-trimethylsilyl enethers undergo condensation with acyl fluorides to afford O-enesters with high yields. The intermediates and final products...

1- and 2-fluoroalkyl carboxylates (1995)

Limat, Dominique, Guggisberg, Yves, Schlosser, Manfred

The 2-fluoroalkyl esters, e.g. FCH2CH2CO2Me are readily accessible by the base-catalyzed acylation of fluorohydrines. A two-step procedure is required to prep. the 1-fluoroalkyl esters: conversion of...

Mechanistic Aspects of Polar Organometallic Chemistry. [In: Tetrahedron, 1994, 50(20)] (1994)

A fluoroisoprenylation sequence employing 2-fluoroalkenal derived azomethines as key intermediates: a stereocontrolled synthesis of 2-fluorogeraniol and 2-fluorofarnesol (1994)

Truong-Nguyen, Thi My Thu, Togo, Hideo, Schlosser, Manfred

Azomethines (Schiff's bases) derived from a,b-unsatd. a-fluoroaldehydes can be deprotonated with lithium diisopropylamide. The resulting \"anions\" or, correctly, 3-fluoro-1-azapentadienyl lithium...

A short and simple access to both enantiomers of epi-b-santalene and (Z)-epi-b-santalol (1994)

Zhong, Guo-fu, Schlosser, Manfred

Epi-b-santalene (I; R = H), readily accessible in both enantiomeric forms, was regio- and stereoselectively converted into (R)-(-)- or (S)-(+)-(Z)-epi-b-santalol (I; R = OH) by consecutive...

How advantageous is the intramolecular aggregation of 1,4-organodilithio compounds? (1994)

Desponds, Olivier, Schlosser, Manfred

1,11-Dilithio-5,5,7,7-tetramethyl-5,7-dihydrodibenz[c,e]oxepin (3; shown as I) is a conformationally confined analog of o,o'-dilithiobiphenyl (1). A temp. variable NMR study of this model compd.,...

The spontaneous cyclodimerization of 2,3-dihydroisoquinolines after base promoted elimination of methanol from 4-methoxy-1,2,3,4-tetrahydroisoquinolines (1994)

Simig, Glyula, Schlosser, Manfred

The reaction of 4-methoxy-1,2,3,4-tetrahydroisoquinolines I (R = MeO, R1 = H; RR1 = OCH2O) with Li diisopropylamide affords dimerization products II. The intermediacy of orthoquinodimethanes and...

A convenient and economic way to produce anhydrous hydrogen bromide (1994)

Wang, Xian Hong, Schlosser, Manfred

Bromide promoted decompn. of tert-Bu bromide in the presence of triphenylphosphine gives, besides isobutene, hydrogen(triphenyl)phosphonium bromide. When heated to approx. 150 DegC in the presence of...

Site selective hydrogen/metal exchange: competition and cooperation between superbases and neighboring groups (1994)

Schlosser, Manfred, Faigl, Ferenc, Franzini, Livia, Geneste, Herve, Katsoulos, Georges, Zhong, Guo Fu

A review with 62 refs. The appropriate choice of a metalating reagent is the key to the optional deprotonation of benzylamine derivs. at a position adjacent to the substituent or the nitrogen bearing...

[4 + 2]-Cycloaddition reactions employing 2-fluoro-2-alkenal N,N-dimethylhydrazones: synthesis of 3-fluoropyridines and dihydro or tetrahydro derivatives thereof (1994)

Ghosh, Somnath, Schlosser, Manfred

N,N-dimethylhydrazones,e.g., CH2:CFCH:NNMe2, prepd. from 2-fluoro-2-alkenals undergo smooth [4 + 2] cycloaddn. reactions with Me acrylate, di-Me acetylenedicarboxylates and quinones. The resulting...

Pyrrolobenzoxazepine ring construction through metalation and electrophilic substitution of N-[2-(hydroxymethyl)phenyl]pyrrole (1994)

Schlosser, Manfred, Faigl, Ferenc

N-[2-(hydroxymethyl)phenyl]pyrrole was found to be amenable to selective a-metalation. Trapping with a variety of electrophilic reagents afforded the expected products with moderate to high yields....

Identification of stereoisomers based on dielectric studies: dipole moments of chloroalkenes and chlorocumulenes (1994)

Bauer, Paul J., Exner, Otto, Ruzziconi, Renzo, Tran Dinh, An, Tarchini, Claudio, Schlosser, Manfred

The use of dielec. measurements to assign mol. configurations was examd. with model compds. of the chloroalkane, chloroalkene and chlorocumulene type. A dielec. microcell is described which allowed...

Metalated fluoropyridines and fluoroquinolines as reactive intermediates: new ways for their regioselective generation (1994)

Shi, Guo-qiang, Takagishi, Sadahito, Schlosser, Manfred

The mixt. of lithium diisopropylamide and potassium tert-butoxide (LIDA-KOR reagent) is a powerful base which can be advantageously employed for the regioselective deprotonation of fluoropyridines...

Site selective substitution of carbamate and carbamoyl protected benzylamines (1993)

Katsoulos, Georges, Schlosser, Manfred

Methoxy- and fluoro-substituted benzylamines can be metalated optionally at the position adjacent to the nitrogen bearing side chain or adjacent to the hetero substituent as a function of the...

N-Phenylpyrrole: a kinetic, though not thermodynamic preference for dilithiation (1993)

Faigl, Ferenc, Schlosser, Manfred

Under appropriate conditions the clean prepn. of either the a-mono-lithiated or the o,a-dilithiated deriv. of N-phenylpyrrole is possible. In the latter case, the first deprotonation occurs at the...

4'-Oxa-a-santalene and 4'-oxa-a-santalol: an olfactory comparison with the analogous natural sesquiterpenes (1993)

Zhong, Guo Fu, Schlosser, Manfred

Allyl type organometallic intermediates allow the prepn. of the 4'-oxa analogs I (R = H, OH, X = O) of a-santalene (I; R = H, X = CH2) and a-santalol (I; R = OH, X = CH2) in a very convenient, regio-...

Polar allyl type organometallics as key intermediates in regio- and stereocontrolled reactions: conformational mobilities and preferences (1993)

Schlosser, Manfred, Desponds, Olivier, Lehmann, Ruth, Moret, Etienne, Rauchschwalbe, Guenter

A review with 64 refs., including discussion of the structural flexibility of organometallic species, the stereochem. of 2-alkenylmetal compds., and the origin of the endo effect. [on SciFinder (R)]

A shortcut to a-santalol (1993)

Schlosser, Manfred, Zhong, Guo Fu

a-Santalol (Z-I) can be prepd. from the readily available 8-bromotricyclene (II) in a one-flask procedure under perfect regio- and stereocontrol. [on SciFinder (R)]

Highly cis-selective Wittig reactions employing a-heterosubstituted ylides (1993)

Zhang, Xin Ping, Schlosser, Manfred

1-Alkenyl chlorides, bromides or iodides, e.g., cis-1-chloro-1-octene, can be obtained with very high cis selectivities by Wittig reactions with a-chloro, a-bromo and a-iodo ylides derived from...

A novel and versatile access to fluorinated carbo- and heterocyclic compounds employing electron-rich fluorodienes as cycloaddition components (1993)

Shi, Guo-qiang, Schlosser, Manfred

The readily accessible 2-fluoro-1-trimethylsiloxy-1,3-dienes undergo Diels-Alder type cycloaddn. with a variety of dienophiles under mild conditions. In this way, fluoro-2-cyclohexenols,...

Improved cis selectivities of carbonyl substituted, stable phosphorus ylides (1993)

Patil, Vijay, Schlosser, Manfred

Tris(2-methoxymethoxyphenyl)phosphine was readily quaternized when treated with Me bromoacetate. The resulting phosphornium salt was deprotonated to give the corresponding ylide...

Synthesis of 1,2-dihydroisoquinoline-3-carbaldehydes. [Erratum to document cited in CA117(15):150854e] (1993)

Schlosser, Manfred, Simig, Gyula

An error in the omission of an author has been cor. Omitted Acknowledgments have also been provided. Only the author error was reflected in the abstr. (the heading) and the index entries. [on...

The Diels-Alder approach to musk odor type arenes (1992)

Shi, Guo Qiang, Cottens, Sylvain, Shiba, Sayed Ahmed, Schlosser, Manfred

The readily accessible 2-halogeno-1-trimethylsilyloxy-1,3-butadienes, e.g. CH2:CRCR1:CHOSiMe3 (R = H, Me; R1 = F, Cl) react smoothly with MeO2CC.tplbond.CCO2Me to afford 4-halophthalic esters, e.g....

Superbases as powerful tools in organic syntheses (1992)

Fluorine and trifluoromethyl substituted anilines: site selective metalation and electrophilic substitution (1992)

A review with 136 refs. on the use of organometallic and other superbases in org. synthesis. [on SciFinder (R)]

Takagishi, Sadahito, Katsoulos, Georges, Schlosser, Manfred

When treated with tert-butyllithium in THF at -50 Deg, N-BOC (tert-butoxycarbonyl) protected fluoroanilines and trifluoromethylanilines, e.g., o-, m-, or p-F3CC6H4NHCO2CMe3, undergo metalation at the...

Does the ipso-carbon chemical shift tell us anything about the structure of phenylated phosphorus compounds? (1991)

Liu, Zi Ping, Schlosser, Manfred

The NMR signals exhibited by the ipso-carbon atoms of a variety of phenylated phosphorus compds., e.g., Ph5P, were found to span over the remarkably wide range of +162 to +117 ppm. Nevertheless,...

The metalation of fluoroanisoles: optional regioselectivity due to metal mediated control (1991)

Katsoulos, Georges, Takagishi, Sadahito, Schlosser, Manfred

2- And 4-Fluoroanisole undergo hydrogen/metal exchange at the position next to the alkoxy moiety if n-BuLi or tert-BuLi is used and at the position next to the halogen atom if the stoichiometric...

gem-Difluorocyclopropenes by [1+2] cycloaddition reactions between difluorocarbene and acetylenes having terminal or internal triple bonds (1991)

Bessard, Yves, Schlosser, Manfred

Difluorocarbene, generated from (bromodifluoromethyl)triphenlphosphonium bromide, underwent cycloaddn. to RC.tplbond.CR1 (R = Ph, hexyl, octyl, R1 = H; R = Pr, R1 = Me, propyl; R = Ph, R1 = Me) to...

The two-fold reaction benchmark applied to the copper catalyzed assembling of 1,w-difunctional hydrocarbon chains (1991)

Schlosser, Manfred, Bossert, Henri

Long-chain hydrocarbons carrying vinyl groups, chlorine atoms or oxygen functions at the terminal positions can be prepd. with excellent yields by copper mediated coupling of alkyl tosylates and...

Optional ortho or alpha hydroxymethylation of alkylarenes (1991)

Guggisberg, Yves, Faigl, Ferenc, Schlosser, Manfred

Treatment of arenes carrying Me or primary alkyl groups, e.g., EtPh, in THF with potassium tert-butoxide activated butyllithium followed by reaction with formaldehyde gives 2-arylalkanols, e.g.,...

A one-pot synthesis of ibuprofen involving three consecutive steps of superbase metalation (1991)

Faigl, Ferenc, Schlosser, Manfred

A one-pot reaction sequence consisting of three consecutive metalation and electrophilic substitution stages starting with p-xylene leads to 2-(4-isobutylphenyl)propanoic acid with a 52% overall...

In the blind spot of diffusion control: 2-fluoroallyl cations and their various possibilities for stabilization (1991)

Bessiere, Yvonne, Bessard, Yves, Kotani, Takayuki, Schlosser, Manfred

Three new model substrates of the chlorofluorocyclopropane type (I, II, and III) were submitted to silver ion-assisted ring opening. No rearrangement, but only fragmentation or direct solvolysis,...

1-Oxa-2,3-cyclohexadiene (\"2H-isopyran\"): a strained heterocyclic allene undergoing cycloaddition reactions with characteristic typo-, regio- and stereoselectivities (1991)

Ruzziconi, Renzo, Naruse, Yuji, Schlosser, Manfred

1-Oxa-2,3-cyclohexadiene (I) can be readily generated by treatment of 5-bromo-3,4-dihydro-2H-pyran with potassium tert-butoxide in the presence of 18-crown-6 and can be trapped with dienes or...

The preparation of pure allyl- and benzyl-type organoalkali intermediates via organotin compounds (1991)

Desponds, Olivier, Schlosser, Manfred

Superbase metalation of alkenes or alkylbenzenes and subsequent condensation with trialkylstannyl chloride affords allyl- or benzyl-type organotin compds. that can be isolated in pure form. Treatment...

8-Methoxyisoquinoline derivatives through ortho-selective metalation of 2-(3-methoxyphenyl)ethylamine (1991)

Schlosser, Manfred, Simig, Gyula

Butyllithium in Et2O smoothly metalates 3-MeOC6H4CH2CH2NHCOCMe3 at the ortho position flanked by the two substituents. Subsequent reaction with DMF followed by acid catalyzed cyclization and redn....

1,(w-1)-Dienes: solvent controlled unilateral or bilateral metalation (1991)

Moret, Etienne, Desponds, Olivier, Schlosser, Manfred

In hexane, i.e. under heterogeneous conditions, 1,(w - 1)-dienes readily undergo double deprotonation to give bis(allylmetal) intermediates. In THF at -75 or -50 Deg, however, only monometalation...

3-Amino-2-arylpropanoic acids by electrophilic substitution of 2-arylethylamines at the benzylic position (1991)

A one-pot synthesis of coumaryl, coniferyl, and sinapyl alcohol (1991)

Title amino acids I (R, R1, R2 = H, OMe) were prepd. from 2-arylethylamines II by a reaction sequence consisting of N-pivaloylation, lithiation at the benzylic position with tert-BuLi, carboxylation,...

Rothen, Laure, Schlosser, Manfred

The side chain of 4-allylphenols was easily deprotonated by BuLi-KOCMe3. Consecutive treatment with FB(OMe)2 and H2O2 afforded the title alcs. I (R = H, R1 = H, OMe; R = R1 = OMe). [on SciFinder (R)]

Catalytic hydrogenolysis of cyclopropanes: metal insertion into a saturated carbon-carbon bond as the key step (1991)

Bessard, Yves, Schlosser, Manfred

Hydrogenolytic ring cleavage of gem-difluorocyclopropanes, e.g. I and II, occurs exclusively at the carbon-carbon bond opposite to the halogen-bearing center and affords mainly gem-difluoroalkanes,...

Fluorine- and trifluoromethyl-substituted toluenes: site selective metalation of aromatic or benzylic positions (1991)

Takagishi, Sadahito, Schlosser, Manfred

At -75 Deg, the superbasic mixt. of BuLi and KOCMe3 metalates 2-, 3-, and 4-FC6H4Me exclusively at an arom. position adjacent to the halogen, as demonstrated by quenching with CO2 to give the...

An easy and versatile access to 8-substituted isoquinolines (1990)

Superbase reactions: the expedient and selective metalation of fluorine- or trifluoromethyl-substituted benzenes (1990)

Lithiation of N-(2,2-diethoxyethyl)benzylamines I (R = Me, PhCH2) and reaction with electrophiles followed by acid-catalyzed cyclization leads to isoquinolines II (R1 = Me, MeO, CH2OH, MeS, Cl, Br,...

Schlosser, Manfred, Katsoulos, Georges, Takagishi, Sadahito

When treated with the superbasic mixt. of butyllithium and potassium tert-butoxide, fluorobenzene, difluorobenzenes, fluoro(trifluoromethyl)benzenes, (trifluoromethyl)benzene and...

Monomeric formaldehyde in ethereal solution (1990)

Schlosser, Manfred, Jenny, Titus, Guggisberg, Yves

Ethereal solns. of monomeric formaldehyde can be conveniently prepd. from paraformaldehyde and p-toluenesulfonic anhydride and offer practical advantages in org. synthesis. [on SciFinder (R)]

Ylide modeling as the key to a cis-selective synthesis of stilbenes (1990)

Tsukamoto, Masamitsu, Schlosser, Manfred

Stilbene type olefins can be prepd. with cis-stereoselectivities approaching 95:5 if tris(2-methoxymethoxyphenyl)phosphine derived ylides are employed and the reaction is carried out at -75 Deg....

Regioselective formation of fluorohydrins and their stereoselective conversion to fluoroolefins (1990)

Suga, Hiroaki, Hamatani, Takeshi, Schlosser, Manfred

When treated with KOCMe3 in THF, fluorohydrin p-tosylates afford fluoro olefins, e.g., Z- or E-Me(CH2)4CF:CH(CH2)4Me, in high yields. Fluorohydrins are readily and stereoselectively accessible by...

Ring opening of gem-dihalocyclopropanes: novel types of 1,4-elimination reactions (1990)

Bessard, Yves, Kuhlmann, Ludwig, Schlosser, Manfred

On treatment with Bu4N+ F-, cyclopropanecarboxylates I (R = Cl; R1 = Cl, F; R2 = OCMe3) undergo Cl-F exchange via cyclopropene intermediates. As a byproduct, H2C:CMeC.tplbond.CCO2CMe3 (II) is formed....

gem-Difluorocyclopropanes: an improved method for their preparation (1990)

Bessard, Yves, Mueller, Ulrich, Schlosser, Manfred

By treatment with Br2CF2 and Ph3P, 4 unfunctionalized olefins, 4 enol ethers and 1 bis-enol ether were converted to gem-difluorocyclopropanes. Thus, RCH:CHOPr (R = H, Me) gave difluorocyclopanes I in...

gem-Difluorocyclopropanes carrying oxygen-functional substituents (1990)

Schlosser, Manfred, Bessard, Yves

Protection of allyl alcs. as acetals, addn. of difluorocarbene and deprotection lead to gem-difluoro(hydroxymethyl)cyclopropanes I (R = Me, Ph) and II. These can be converted to potential pyrethroid...

About the internal mobility of simple and resonance stabilized phosphorus ylides (1990)

Liu, Zi Ping, Schlosser, Manfred

Triphenylphosphoniomethanide and alkyl-substituted analogs are torsionally unrestricted even at -100 Deg whereas the temp. dependence of the rotation around the Ca, Ph axis in...

Selective mono- or dimetalation of arenes by means of superbasic reagents (1990)

Schlosser, Manfred, Choi, Jung Hoon, Takagishi, Sadahito

If employed in THF, stoichiometric amts. of BuLi and KOCMe3 react with benzene to give clean monometalation. In hexane suspension, however, considerable amts. of meta and para-disubstituted...

Vicinal bromofluoroalkanes: their regioselective formation and their conversion to fluoro olefins (1990)

Suga, Hiroaki, Hamatani, Takeshi, Guggisberg, Yves, Schlosser, Manfred

Reaction of alkenes with N-bromosuccinimide and Et3N.3HF produces vic-bromofluoroalkanes in high yields. As long as the addn. to the C:C bond is sterically unhindered, Br and F get attached with very...

About the structure of phosphorus ylides: electron distribution and geometry (1990)

Schlosser, Manfred, Jenny, Titus, Schaub, Bruno

Using 13C-chem. shifts as a probe for the electronic environment of carbon centers, triphenylphosphoniomethanide, the model case of a reactive phosphorus ylide, have much more zwitterion than PC...

Facile isomerization of oxiranes to allyl alcohols by mixed metal bases (1990)

Mordini, Alessandro, Ben Rayana, Ezzedine, Margot, Christian, Schlosser, Manfred

The mixt. of LiN(CHMe2)2 and KOCMe3 (LIDAKOR reagent) promotes smooth ring opening of oxiranes to afford allyl alcs. with good to excellent yields. Internal epoxyalkanes and large-sized...

The enigmatic 1J(CH) coupling constants of allyl-type organometallic compounds (1990)

Schlosser, Manfred, Lehmann, Ruth, Jenny, Titus

A new attempt has been made to identify the factors responsible for the abnormally small one-bond C, H coupling consts. obsd. for allyl, pentadienyl and heptatrienyl compds. of Li and K. In-plane...

a-Fluoro- and a,a-difluoroalkanals by substitution of vicinal bromofluoroalkanes and subsequent Pummerer rearrangement (1990)

Suga, Hiroaki, Schlosser, Manfred

2-Fluoro- or 2,2-difluoro-1-bromoalkanes readily undergo nucleophilic substitution by sodium thiophenolate to give 2-fluoro- or 2,2-difluoroalkyl Ph sulfides. The latter can be oxidized to the...

Mixed metal bases as promoters of 1,4-eliminations (1990)

Margot, Christian, Matsuda, Hiroyuki, Schlosser, Manfred

When treated with the LIDAKOR mixt., allyl type ethers very readily undergo 1,4-elimination to afford conjugated dienes (E)-H2C:CHCH:CH(CH2)4Me, H2C:C(:CH2)CH2CH2CH:CMe2, H2C:CHCH:CHOMe. In typical...

1,2-elimination of alcohol from homoallyl ethers under the influence of mixed metal bases (1990)

Margot, Christian, Rizzolio, Michele, Schlosser, Manfred

Lithium diisopropylamide in the presence of catalytic amts. of potassium tert-butoxide smoothly converts homoallyl or homobenzyl type ethers to dienes or styrenes. g,d-Unsatd. acetals give 1,3-dienyl...

Novel ortho-alkoxy-substituted phosphorus ylides and their stereoselectivity in Wittig reactions (1990)

Jeganathan, Suruliappa, Tsukamoto, Masamitsu, Schlosser, Manfred

The stereochem. of the reactions between tris(2-methoxymethoxyphenyl)phosphonioethanide, -butanide (I) and -phenylmethanide and a variety of aldehydes was investigated. Ylides having a b-unbranched...

Convenient method for the synthesis of N-alkyl-substituted 4-hydroxy-1,2,3,4-tetrahydroisoquinolines (1990)

The Wittig rearrangement as a practical method for aldehyde synthesis (1989)

Title compds. I [R = alkyl, propargyl, (un)substituted benzyl] and II (R = Me, CH2Ph, CH2C6H4Cl-2) were prepd., usually in >=50% yield, by successive treatment of alkoxy-substituted...

Schlosser, Manfred, Strunk, Sven

If the rearrangement of metalated allyl ethers, e.g., I, is accomplished in the presence of potassium tert-butoxide, primary alkyl groups preferentially migrate to the unsubstituted allylic terminus...

Attempted and accomplished syntheses of a few monofluorinated chrysanthemic acid derivatives (1988)

Cottens, Sylvain, Schlosser, Manfred

A sulfone mediated approach presumably did produce Me a-fluorochrysanthemate I but, if formed, the latter immediately underwent dehydrofluorination under the strongly basic reaction conditions. The...

1-(Triphenylmethyl)allylpotassium: conformational preference and [1,2]-rearrangement (1988)

Moret, Etienne, Fuerrer, Juerg, Schlosser, Manfred

Upon treatment with the superbasic 1:1 mixt. of BuLi and Me3COK, cis- and trans-1,1,1-triphenyl-2-butene as well as 4,4,4-triphenyl-1-butene undergo a hydrogen/metal exchange to afford...

o-Selective metalation and electrophilic substitution of benzylamine derivatives (1988)

A stereocontrolled access to vicinal difluoroalkanes (1988)

N-Pivaloylbenzylamines and derivs. [e.g., 2,4-R(MeO)C6H4CH2NHCOCMe3, I, R = H] undergo smooth ortho-metalation when treated with two equivs. of an organolithium reagent. Subsequent carboxylation or...

Hamatani, Takeshi, Matsubara, Seijiro, Matsuda, Hiroyuki, Schlosser, Manfred

An expedient method for the prepn. of diastereomerically and, by extension, even enantiomerically pure vicinal difluoroalkanes is described. The two fluorine atoms are introduced in two consecutive...

Hydrogen fluoride abstraction from vicinal difluoroalkanes: reaction conditions and syn/anti-stereoselectivity (1988)

Matsuda, Hiroyuki, Hamatani, Takeshi, Matsubara, Seijiro, Schlosser, Manfred

vic-Difluoroalkanes are as inert as monofluoroalkanes toward NaOMe in MeOH. Stronger bases, however, can perform dehydrofluorinations relatively smoothly. KOCMe3 in THF at 75 Deg acts exclusively by...

Base-promoted elimination of hydrogen fluoride from alkyl fluorides: reactivity and stereochemistry (1988)

Matsubara, Seijiro, Matsuda, Hiroyuki, Hamatani, Takeshi, Schlosser, Manfred

The alcoholate-promoted dehydrohalogenation of 5-nonyl fluoride and cyclododecyl fluoride, typical straight-chain and, resp., medium-size cyclic substrates, leads to cis- and trans-alkenes in an...

Superbases for organic synthesis (1988)

Elimination from mechanistic and synthetic viewpoints (1988)

A review with 70 refs. LICKOR mixts. of organolithium reagents and bulky potassium alcoholates allow the smooth metalation and subsequent electrophilic substitution of low acidity hydrocarbons, in...

Ring tension, hydrocarbon acidity, and new super-bases (1986)

A review with 30 refs. Topics include the prerequisites for and limits of concertedness, the effect of ion-incompatible reaction conditions, and the synthetic potential of dehydrogenation and ether...

Schlosser, Manfred, Hartmann, Juergen, Staehle, Manfred, Kramar, Jaroslav, Walde, Annelies, Mordini, Alessandro

Addn. of di-Na pinacolate or KOCMe3 increased the transmetalating power of pentylsodium in alkane solvents. Some hydrocarbons thus metalated were Me3CCH:CH2, camphene, bicyclo[2.2.2]octene,...

Metalation of olefinic positions in norbornadiene: enhancement and attenuation of kinetic CH-acidities by a neighboring enesilane moiety (1986)

Mordini, Alessandro, Schlosser, Manfred

When treated with BuLi in the presence of Na or K tert-butoxide, 2-(trimethylsilyl)- and 2-(triethylsilyl)norbornadiene undergo H/metal-exchange mainly at the 5-position. The latter position is...

Enhanced cis-selectivities in olefination reactions employing ylides with modified stationary groups (1986)

Schaub, Bruno, Jeganathan, Suruliappa, Schlosser, Manfred

Whereas triphenylphosphonioethanide manifests unsatisfactory cis-selectivities (84.0-95.5%), tris(o,o'-difluorophenyl)- and tri-o-tolylphosphonioethanide react with aliph. or arom. aldehydes and,...

Practical guidance for obtaining optimum cis-selectivities in Wittig reactions with triphenylphosphonio-alkanides (1986)

Schlosser, Manfred, Schaub, Bruno, De Oliveira-Neto, Jose, Jeganathan, Suruliappa

The crucial role is played by the base, the solvent, and the temp. in detg. the stereochem. outcome of salt-free olefination reactions. Under optimized conditions unprecedented cis-selectivities are...

An efficient synthesis of (2S,3R)- and (2S,3S)-sphingosine (1985)

Obayashi, Michio, Schlosser, Manfred

A straightforward sequence of reactions allowed the conversion of D-(+)-mannose and D-(+)-ribono-1,4-lactone into erythro-(2S,3R)- and threo-(2S,3S)-sphingosine, resp. [on SciFinder (R)]

Hetero-atom effects on kinetic acidities: the metalation of 1-methylcyclohexene and its 4-aza- and 4-oxa-analogs (1985)

Moret, Etienne, Schneider, Philippe, Margot, Christian, Staehle, Manfred, Schlosser, Manfred

Hexane suspensions of Me3SiCH2K or BuLi/Me3COK deprotonated 1-methylcyclohexene almost exclusively at the Me group. In contrast 1,4-dimethyl-1,2,3,6-tetrahydropyridine and...

Acidity enhancement through homoconjugation: selective introduction of sodium into olefinic positions (1985)

Staehle, Manfred, Lehmann, Ruth, Kramar, Jaroslav, Schlosser, Manfred

When treated with BuLi and Me3CONa, both norbornadiene and norbornene underwent a H/Na-exchange at the 2-position. The diene, however, reacted approx. 30 times faster with Me3SiCl....

Solvent-controlled additions of organotitanium reagents to olefinic double bonds (1985)

Moret, Etienne, Schlosser, Manfred

Under carefully chosen working conditions (solvent, temp.), methyltitanium reagents smoothly convert homoallyl alcs. having a terminal double-bond into (E)-3-penten-1-ols, whereas nonterminal...

New evidence for and new reactions of ortho-lithio ylides (1985)

Schaub, Bruno, Schlosser, Manfred

Although a-lithio ylide Ph3P+C-HBr was generated from [Ph3PCH2Br]Br through halogen-metal exchange, the reaction of Ph3P+C-H2 with Me3CLi or Me2CHCH2Li produces the o-lithio ylide I nearly quant. I...

A regio- and stereocontrolled access to 2,4-dienols by amide/alcoholate-promoted ring-opening of dihydropyrans (1985)

Margot, Christian, Schlosser, Manfred

Dihydropyrans I (R = R1 = H, R2 = H, Me, CH2CH2CH:CMe2; R = Me, CH2CHMe2, R1 = H, R2 = Me; R = R2 = H, R1 = CH:CMe2), when treated with LiN(CHMe2)2-KOCMe3, underwent smooth ring cleavage through...

The betaine-ylide route to trans-alkenols (1985)

Schlosser, Manfred, Huynh Ba, Tuong, Schaub, Bruno

(E)-RCH:CH(CH2)nOH (n = 2,3,5,7; R = Et, pentyl, hexyl, E-CH:CHMe) were obtained in 69-78% yield in a 1-pot reaction by treating HO(CH2)nCH2P+Ph3 Br- with PhLi in tetrahydrofuran-EtiO, followed by...

A new stereoselective synthesis of (Z)-9-tricosene, the sex attractant of the common housefly (1985)

Moiseenkov, A. M., Schaub, Bruno, Margot, Christian, Schlosser, Manfred

Muscalure (9/tricosene) was prepd. very readily by an instant-ylid reaction of nonanal with Ph3P:CH(CH2)12Me or of (Z)-Me(CH2)7CH:CHCH2OAc with BrMg(CH2)11Me. (Z)-9-Tricosene was formed in a highly...

The ylide route to fluorodienes (1984)

Kondo, Kazumi, Cottens, Sylvain, Schlosser, Manfred

Ylides Ph3P+C-RR1 (R = H, Me; R1 = OMe, Cl, Me, Pr, Ph, CO2Me) underwent Wittig reaction with fluoroalkenals MeCR2:CFCHO (R2 = H, Me) to give 52-95% MeCR2:CFCH:CRR1. This reaction occurred at approx....

Selective syntheses with organometallics. Part XI. An efficient synthesis of a,b-unsaturated aldehydes by a four-carbon unit extension of Grignard reagents (1984)

Cloux, Roland, Schlosser, Manfred

Oxirane I, prepd. by epoxidn. of (EtO)2CHCH2CH:CH2, reacted with Grignard reagents in the presence of catalytic CuBr to give 78-92% b-hydroxyacetals (EtO)2CHCH2CHR1OH [II; R1 = CH2CMe3, CH2CHMeEt,...

A diastereoselective synthesis of both quercus lactone isomers employing allyl-type organometallics as key intermediates (1984)

Moret, Etienne, Schlosser, Manfred

Consecutive treatment of endo-butenylpotassium or endo-1-(tetrahydropyranyloxy)-exo-butenyllithium with FB(OMe)2 and pentanal at -75 Deg affords an erythro- and, threo-adduct, resp., which on...

ortho-Lithiation of triphenylphosphonio-methylide and, also, triphenylphosphine oxide (1984)

Schaub, Bruno, Jenny, Titus, Schlosser, Manfred

Treating Ph3P+C-H2 with RLi (R = Me, Bu) gave mainly RPh2P+C-H2 via extensive ligand exchange whereas R1Li (R1 = MeEtCH, Me3C) reacts to give o-lithiated Ph2(o-LiC6H4)P+C-H2. Ph3PO is also...

Facile and selective metalation of 7-dehydrocholesterol (pro-vitamin D3) (1984)

Moret, Etienne, Schlosser, Manfred

Successive treatment of 7-dehydrocholesterol (I) with Me3SiCH2K in THF, dry ice, mineral acid, and diazomethane gives a regioisomerically pure, homoconjugated ester II as a diastereomeric mixt., the...

Organofluorine compounds. Part XIII. The halide-promoted fragmentation of 1-chloro-1-fluoro-2-(a-silylaklyl)cyclopropanes: a new entry to fluorodienes (1984)

Schlosser, Manfred, Dahan, Rachel, Cottens, Sylvain

When heated in the presence of Bu4N+.X- (X = F, Cl), 1-chloro-1-fluoro-2-(trimethylsilyl)methylcyclopropanes I (R = H, Me; R1 = Me, Et) undergo smooth ring-opening fragmentation to give...

Facile hydrogen/metal exchange between butylpotassium and saturated ethers (1984)

Lehmann, Ruth, Schlosser, Manfred

At temps. between -100 and -40 Deg, lithium salt-free butylpotassium (prepd. from dibutylmercury) readily metalates satd. ethers such as Me2O or THF. [on SciFinder (R)]

The super-basic butyllithium/potassium tert-butoxide mixture and other LICKOR reagents (1984)

Schlosser, Manfred, Strunk, Sven

The reactivity pattern of the butyllithium/potassium tert-butoxide mixt. with cumene differs significantly from that of BuK and thus disproves the claimed identity of these two reagents. [on...

Wittig-Reaktion von Triphenylphosphonio-alkyliden mit substituierten Benzaldehyden : Hammett-Beziehung und teilweise Reversibilität der Addukt-Bildung (1983)

Piskala, Alois, Rehan, Abdul Hamid, Schlosser, Manfred

The kinetics and stereochem. of the Wittig reaction of Ph3P:CHR (R = H, Me) with R1C6H4CHO (R1 = H, p-MeO, p-Me, p-, m-Cl, p-cyano, p-F3C) to give RCH:CHC6H4R1 was investigated. The reaction...

The Wittig reaction: 30 years later (1983)

Schlosser, Manfred, Oi, Ryu, Schaub, Bruno

New and old ylide reactions are described and their mechanisms examd. A review with 12 refs. [on SciFinder (R)]

Pheromones as test targets for stereoselective carbon-carbon linking methods (1983)

Fujita, Katsuramaru, Cloux, Roland, Tuong, Huynh Ba, Moret, Etienne, Schaub, Bruno, Schlosser, Manfred

Review with 30 refs. [on SciFinder (R)]

SCOOPY and oxirane reactions: a-lithio-ylides vs. conventional ylides (1983)

Schlosser, Manfred, Huynh Ba, Tuong, Respondek, Johannes, Schaub, Bruno

Ph3P:CH2 reacted with epoxides I (R = H, Me, vinyl; R1 = H, Me) or cyclohexene oxide in the presence of 1.2 equiv LiX (X = Br, iodo, BPh4) to give Ph3P+CH2CH2CRR1OH X- or 83% trans-II. Similarly,...

Reazione di Wittig (1983)

Instant-Ylid: ein lagerfähiges und gebrauchsfertiges Wittig-Reagenz (1982)

Schlosser, Manfred, Schaub, Bruno

Mixts. prepd. from alkyltriphenylphosphonium bromides and powd. NaNH2 were stored indefinitely. Upon addn. of an ethereal solid, however, they immediately generated the ylide, which then reacted with...

Titanium-mediated and neighboring-group-assisted d-methylation of homoallyl alcohols: a new regio- and stereoselective carbon-carbon linking reaction (1982)

Fujita, Katsuramaru, Moret, Etienne, Schlosser, Manfred

Upon treatment with Me2TiCl2 or Me3Al in the presence of TiCl4, an H atom at the olefinic 4-position is replaced by a Me group. Terminal homoallyl alcs. afford E isomers. If the double bond is...

Carbon-13 NMR spectra of lignins. 9. Spin-lattice relaxation times (T1) and determination of interunit linkages in three hardwood lignins (Alnus glutinosa, Corylus avellanus and Acer pseudoplatanus) (1982)

Nimz, Horst H., Nemr, Michel, Schmidt, Peter, Margot, Christian, Schaub, Bruno, Schlosser, Manfred

The spin-lattice relaxation time (T1) for the aliph. C atoms in the C3 side chains of acetylated MWL from C. avellana was below 0.5 s, while C atoms of substituted arom. carbonyl and Me in methoxy...

"Isoretinol" and retinal: an unorthodox but simple route to the vitamin A series (1982)

Ruzziconi, Renzo, Schlosser, Manfred

\"Isoretinol\" I was prepd. in 55% yield by methylation of II, obtained by reaction of III with the (chlorodihydrofuryl)copper IV. Oxidn. of I with Me2SO contg. N,N'-dicyclohexylcarbodiimide gave a...

Selective syntheses with organometallics. Part X. A convenient and diastereoselective route to homoallyl alcohols: addition of (Z)- or (E)-alkenyldimethoxyboranes to aldehydes (1982)

Fujita, Katsuramaru, Schlosser, Manfred

Addn. of alkenyldimethoxyboranes to EtCHO or BzH proceeded almost completely stereospecifically; e.g., (Z)-2-butenyldimethoxyborane and EtCHO gave 62% R*,R*-EtCH(OH)CHMeCH:CH2 of 96% isomer purity;...

Cis selectivity of salt-free Wittig reactions: a "Leeward Approach" of the aldehyde at the origin? (1982)

Schlosser, Manfred, Schaub, Bruno

In THF at 25 Deg, Et3P:CHMe reacts with heptanal, Me3CCHO, PhCHO and p-ClC6H4CHO to afford, after 2-4 h, the corresponding olefins in 89-99% yield. In each case the trans isomer prevails, cis/trans...

Nonplanar structures of allyl- and pentadienylmetal compounds: folding for better charge distribution? (1982)

Schlosser, Manfred, Staehle, Manfred

The 2J (13C, H), a measure of bond angle in CH2:CHCH2R (R = MgBr, Li, Na, K), (Z)- and (E)-MeCH:CHCH2K, CH2:CHCH:CHCH2R (R = Li, K), or (E)-hexadienyllithium, is used to assign the % s character in...

A Stereocontrolled Synthesis of the Pheromone 4-Methyl-3-heptanol : Novel and Selective CC-Linking Reactions (1982)

Schlosser, Manfred, Fujita, Katsuramaru

The Scolytus multistriatus aggregation pheromone (S,S)-4-methyl-3-heptanol was prepd. via 2 stereoselective steps. Reaction of (Z)-2-butenyl potassium with FB(OMe)2 at -75 Deg gave...

Base Promoted 1,4-Elimination Reactions : On the Origin of an Eventual syn-Stereoselectivity (1981)

Schlosser, Manfred, Tarchini, Claudio, Tran Dinh, An, Ruzziconi, Renzo, Bauer, Paul J.

Rate ratios were obtained for the base-catalyzed 1,4-dehydrochlorination of (E)- and (Z)-Me3CCCl:C:C:CClCMe3 to give Me3CC.tplbond.CC.tplbond.CCMe3. In the KOMe/MeOH or KOCMe3/Me2SO systems the...

Alcoholate Clusters ("Aggregates") and Their Role in Alkyne Forming Elimination Reactions (1981)

Schlosser, Manfred, Tran Dinh, An

Kinetic data for the dehydrochlorination of (E)- and (Z)-MeCH:CClC.tplbond.CCMe3 by KOCMe3 (I) in different solvents suggested that I assocs. participated in a push-pull, conveyor-belt mechanism....

Neue 13C-spektroskopische Untersuchungen zur Struktur von Allylmetall-Verbindungen (1981)

Staehle, Manfred, Schlosser, Manfred

High-resoln. 13C NMR spectra of terminally monodeuterated alkali metal and alk. earth metal allyl compds. confirm earlier structure assignments: allylmagnesium bromide exists in a s-covalent...

Die Strukturdynamik von Pentadienylmetall-Verbindungen mit endständiger Alkyl-Gruppe : zugleich "stereoselektive" und "stereodefensive" Synthese eines natürlichen Riechstoffes (1980)

Bosshardt, Herbert, Schlosser, Manfred

Stereospecific metalation of (Z)- and (E)-1,4-decadiene with BuLi or BuLi-Me3COK followed by dimethoxyborylation and oxidn. gave (Z,E)-, (E,Z)-, and (E,E)-isomers of 2,4-decadien-1-ol (I), and the...

Regioselektive Metallierung des Phenylcyclopropans sowie leichte Anlagerung des 1-Phenylcyclopropylkaliums an Äthylen (1980)

Schlosser, Manfred, Schneider, Philippe

Whereas pentylsodium in pentane mainly promotes a hydrogen/metal exchange reaction at the m- and p-position of phenylcyclopropane (I), both BuLi-KOCMe3 and Me3SiCH2K in THF convert I into...

Durch Bromierung ausgelöste Umlagerung tertiärer Allylalkohole : Der Einfluß eines Fluor-Substituenten auf Reaktionsgeschwindigkeit und Reaktionsverlauf (1980)

Nagakura, Isao, Savary, Dang Ngoc Hue, Schlosser, Manfred

Reaction of Me3CCMe(OH)CR:CH2 (I; R = H) with Br2 or NBS in aq. medium resulted in rearrangement, yielding ketones Me3CCOCHMeCH2Br and MeCOCR(CH2Br)CMe3 (III) and the oxirane II. With I (R = F, Me),...

Die Stereochemie der fragmentierenden Enthalogenierung von 1-Chlor-1-fluor-2-(1-halogenalkyl)cyclopropanen (1980)

Spahic, Bojana, Schlosser, Manfred

A no. of model substrates, e.g., I (X = Br, iodo) (anti/cis), were submitted to Zn-promoted fragmentation and the compn. of the resulting mixt. of isomeric fluorodienes was detd. The exocyclic...

Ein einfacher und allgemeiner Zugang zu 2-Fluor-1,3-dienen (1980)

Spahic, Bojana, Truong Thi My, Thu, Schlosser, Manfred

Fluoroalkadienes were prepd. by Zn-catalyzed ring cleavage of 1-chloro-1-fluoro-2-halomethylcyclopropanes, obtained by treating haloalkenes with FCHCl2. Thus, ClCH2CH:CMeEt was treated with FCHCl2 to...

"3-Fluorisopren" (2-Fluor-3-methyl-1,3-butadien) und einige heterosubstituierte Abkömmlinge (1980)

Schlosser, Manfred, Spahic, Bojana

CH2:CFCMe:CHR (I, R = cyano, SO2Ph) were prepd. by ring cleavage of the cyclopropanes II (R = cyano, SO2Ph), prepd. by treating methallyl chloride with FCHCl3 and substitution in I (R = Cl). I (R =...

Allylic Compounds of Magnesium, Lithium and Potassium : sigma- oder pi-Structures ? (1980)

Schlosser, Manfred, Staehle, Manfred

The s- vs. p-character of title allylmetal compds. was studied via 13C NMR of R2CR1:CRCH2N (R = H, Me2CH, Me3C, R1 = R2 = H; R = R1 = H, R2 = Me; R = H, R1 = R2 = Me; M = Li, K, MgBr) and of...

A Facile Route to a Sensitive Terpene Alcohol : Regio-unselective Metalation of alpha-Terpinene as Key Step (1980)

Schlosser, Manfred, Bosshardt, Herbert, Walde, Annelis, Stoehle, Manfred

Treatment of a-terpinene (I, R = H) with BuLi-KOCMe3 followed by FB(OMe)2 and then alk. H2O2 soln. gave 44% anthemol (I, R = OH). The metalation step of a-terpinene presumably gave 3 pentadiene-K...

Metalated 2-Alkenyl- and 1,2-Alkadienyl 2-Tetrahydropyranyl Ethers : Versatile Building Blocks for Furan Syntheses (1979)

Staehle, Manfred, Schlosser, Manfred

Me3CLi metalated LiOCH2C:CCH2OTHP (THP = tetrahydro-2-pyranyl) quant. to LiOCH2CLi:C:CHOTHP which was treated with MeOH, Me(CH2)5I, or PhCH2Cl to give LiOCH2CR:C:CHOTHP [I; R = H, (CH2)5Me, CH2Ph]....

New Evidence for Zwitterionic Intermediates in the Wittig Reaction (1979)

Schlosser, Manfred, Tuong, Huynh Ba

Addn. of Me3COLi to Ph3P+C-MeCH2OLi at 25 Deg gave 2-methylallyl alc. in 80%' yield via a postulated oxaphosphetane intermediate. [on SciFinder (R)]

Eine ungewöhnliche Chlorwasserstoff-Abspaltung : syn-Eliminierung aus einem sterisch behinderten, aber frei drehbaren Halogenkohlenwasserstoff (1979)

Schlosser, Manfred, Tran Dinh, An

meso-Me3CCHClCHClCMe3 undergoes base-promoted dehydrochlorination in a syn- or anti-periplanar manner, affording (Z)-Me3CCCl:CHCMe3 (I) and the thermdn. less stable (E)-I, resp.; the reaction is...

Metalation of Pyrans and Dihydropyridines : When is an 8pi-System Cost Effective ? (1979)

Schlosser, Manfred, Schneider, Philippe

The pyrans I (R = Me, H; R1 = H) with BuLi/KOCMe3 or KSiMe3 gave the 2-metalated derivs. I (R1 = K), which reacted with alkyl halides to give I (R = H, Me; R1 = Me, Et, SiMe3, CH2SiMe3); thus the...

Hydroxyd-bewirkte Halogenwasserstoff-Abspaltungen aus vic-Dihalogeniden unter heterogenen Bedingungen : Reaktionssteuerung dank überraschender Solvens- und Metall-Einflüsse (1979)

Tarchini, Claudio, Tran Dinh, An, Jan, Gerald, Schlosser, Manfred

Selective elimination of either one or two mols. of hydrogen halide from vicinal dihalides can be conveniently achieved by employing solid NaOH or KOH in the presence of solvents such as glycol di-Me...

alpha-Hydroxymethylen-verlängerte Aldehyde durch schonende Reduktion von Cyanhydrinen (1978)

Schlosser, Manfred, Brich, Zdenek

The OH group in cyanohydrins RR1C(OH)CN [R = Me2CH, R1 = H; R = R1 = Me; RR1 = (CH2)4, (CH2)5] was protected with EtOCH:CH2 to give RR1C(CN)OCHMeOEt, which were then reduced by NaAlH2(OCH2CH2OMe)2 to...

2-Methylpentadienyl- and 2,4-dimethylpentadienylpotassium: first examples of U-shaped, though open-chain, organometallics (1978)

Schlosser, Manfred, Rauchschwalbe, Guenter

The U-shaped structures of the title compds. I (R = H, Me) were elucidated by the dimethoxyboration-oxidn. procedure to II (R = H, R1 = Me; R = Me, R1 = H, and R = R1 = Me). [on SciFinder (R)]

Selective syntheses with organometallics. 7. (Z)-2-Ethoxyvinyllithium: a remarkably stable and synthetically useful 1,2-counterpolarized species (1978)

Lau, Kreisler S. Y., Schlosser, Manfred

(Z)-EtOCH:CHLi (I) reacts with carbonyl compds. as an acetaldehyde anion equiv. The exceptional stability of I is attributed mainly to an intramol. solvation mechanism. That the cis disposition of...

Base-induced elimination reactions. VII. Hydroxide-promoted elimination reactions: alkyl halides as substrates (1977)

Schlosser, Manfred, Tarchini, Claudio

HCl and HBr were easily abstracted from secondary and tertiary alkyl halides by KOH in tetraglyme, but primary alkyl halides yielded approx. equal amts. of elimination and substitution products...

Eine einfache Synthese von Rosenfuran und verwandten Verbindungen (1977)

Ly, Nguyen Dinh, Schlosser, Manfred

3-Methyl-2-geranylfuran (I, R = CH2CH:CMeCH2CH2CH:CMe2, R1 = Me) was prepd. by treating I (R = Li, R1 = Br) [prepd. from I (R = H, R1 = Br) and (Me2CH)2NLi] with BrCH2CH:CMeCH2CH2CH:CMe2 and...

Phosphor-Betaine als Wittig-Zwischenstufen : Es gibt sie doch ! (1977)

Schlosser, Manfred, Huynh Ba, Tuong, Tarchini, Claudio

Phosphorus ylides combine with carbonyl compds. to give zwitterionic betaines as detectable intermediates of the Wittig reaction, provided that the neg. charge on the O atom was substantially reduced...

Syntheses of organofluorine compounds. VIII. Solvolytic ring-opening of alkoxychlorofluorocyclopropanes: a ready access to fluorinated a,b-unsaturated aldehydes and ketones (1977)

Bessiere, Yvonne, Dang Ngoc Hue, Savary, Schlosser, Manfred

1-Chloro-1-fluorocyclopropanes [I; R, R1, R2, R3 = H, OMe, Me, Me; Me, OMe, H, H; H, OMe, Me, Me2CH(CH2)3; H, OMe, Me, Me2C:CHCH2CH2; Me, Me, H, MeOCH:CMeCH2CH2; H, OEt, H, Me] were easily prepd. by...

Selective syntheses with organometallics. VI. Capricious stereoselectivities of alkenylpotassium formation under kinetic and thermodynamic control. Oxygen-triggered configurational equilibration of an allyl type organometallic compound (1977)

Staehle, Manfred, Hartmann, Juergen, Schlosser, Manfred

Metalation at the allylic site (Me group) of (Z)-RCH:CHMe (R = alkyl) is more rapid than with the E-isomers regardless of the configuration in which the resultant organometallic is more thermodn....

Syntheses of organofluorine compounds. VII. Structurally biased 2-fluoroallyl cations as generated (or not generated) in cyclopropane ring-opening reactions (1977)

Schlosser, Manfred, Bessiere, Yvonne

The Ag ion-catalyzed ring-opening of a 1:4 mixt. of syn- and anti-cyclopropanes I and II gave the expected mixt. of CH2:CFC(OH)MeCMe3 and (Z)-MeC(CMe3):CFCH2OH in 56 and 19% yield, resp. Under...

Ilidi (1977)

2-Alkenyl anions and their surprising endo preference. Facile and extreme stereocontrol over carbon-carbon linking reactions with organometallics of the allyl type (1976)

Schlosser, Manfred, Hartmann, Juergen

On structural equilibration, butenyl sodium, potassium and cesium strongly favor the cis (endo) configuration over the extended form. The cis-trans ratios vary from 93:7 to 96:4 and 99.9:0.1 in the...

Solvolyse de Chlorofluorocyclopropanes (1976)

Bessiere, Vyonne, Schlosser, Manfred

The acetolysis of 1-chloro-1-fluorocyclopropanes I [R = Me, (CH2)3OAc] with AgOAc in Ac2O contg. BF3 gave the resp. RCMe(OAc)CF:CH2 (II) initially, and the II eventually rearranged to the more stable...

Trimethylsilylmethyl-kalium und andere Spitzenkönner unter den Metallierungsmitteln (1976)

Hartmann, Juergen, Schlosser, Manfred

For the metalation of allylic and benzylic positions Me3SiCH2K is the most powerful reagent. BuLi in the presence of KOCMe3, however, can usually replace it. Olefinic and cyclopropane H atoms are...

Ene-sulfides as reaction partners of organometallic compounds (1976)

Muthukrishnan, Ramamurthi, Schlosser, Manfred

Whereas Ph substituted-vinyl ethers undergo lithiation at either an allylic C or the C attached to the O, the sulfides are lithiated predominantly at the C attached to the S. [on SciFinder (R)]

Phosphor-Ylide (1976)

Prescriptions and ingredients for controlled carbon-carbon bond formation with organometallic reagents (1975)

Eine Carben/Carbenoid-Kaskade und "Hypermechanismen" (1975)

Merits and drawbacks of known C-C linking procedures, such as condensation, addn., and isomerization reactions, are outlined. Two novel methods are discussed in more detail: the Cu-catalyzed...

Schlosser, Manfred, Spahic, Bojana, Le Van, Chau

The cycloaddn. of dihalocarbenes, formed via reaction of tetrahalomethane-trihalomethane pairs with MeLi, with Me2C:CHEt was studied. Ratios of cycloaddn. versus consecutive substitution reactions,...

Darstellung und Abwandlung von Chlorfluorcyclopropanen : Ein gezielter Zugang zu Fluorallylalkoholen (1975)

Schlosser, Manfred, Le Van, Chau

Cycloaddn. of ClFC.bul. to olefins RR1C:CHR2 (R = alkyl or substituted alkyl, e.g., Et, ClCH2, AcOCH2CH2CH2; R1 = H, Me, Et; R2 = H, Me) gave 1-chloro-1-fluorocyclopropanes; these were acetolyzed to...

1-Fluor-1-organyl-cyclopropane und andere Cyclopropan-Derivate durch Anlagerungsreaktion von "Nachfolge-Carbenen" (1975)

Schlosser, Manfred, Le Van, Chau, Spahic, Bojana

Reaction of HCClF2 (I) or Cl2CF2 (II) with MeLi and an olefin gave 1-fluoro-1-methylcyclopropanes in fair yields. Thus, reaction of II with EtCH:CMe2 and MeLi at -78 Deg gave syn- and anti-III and...

Gezielte Hydroxylierung von Allylstellungen (1975)

Rauchschwalbe, Guenter, Schlosser, Manfred

Treatment of a-pinene with Me3COK and BuLi gave intermediate I which was oxidized with H2O2 to give 42% (1S,5R)-myrtenol (II, X = OH) and .apprx.1% (1R,3R,5S)-trans-pinocarveol (III, X = OH)....

Insertion of a Carbon Atom into Olefinic Double Bonds : Synthesis of Fluorodienes and Fluoroalkenes (1975)

Schlosser, Manfred, Spahic, Bojana, Tarchini, Claudio, Le Van, Chau

Reaction of chlorofluorocarbene with CH2:CMeCH2Cl gave I (R = Cl), which was treated with NaI to give I (R = I). Reaction of this with Zn gave CH2:CFCMe:CH2, which, on treatment with Br, gave...

Zum Ablauf der Wittig-Reaktion : zyklische oder ringoffene Zwischenstufen ? (1975)

Schlosser, Manfred, Piskala, Alois, Tarchini, Claudio, Huynh Ba, Tuong

Low temp. 31P NMR indicated that the reaction of Ph3P+C-RR1 (I, R = R1 = H, Me) with R2COR3 (R2 = R3 = H; R2 = Ph, R3 = H) under salt free conditions gave the corresponding oxaphosphetane (II); in...

Metallierung allylständiger Methylen- und Methin-Gruppen (1975)

Hartmann, Juergen, Schlosser, Manfred

Metalation of cyclohexene by Me3SiCH2K, then treatment with ethylene oxide gave 83% 2-cyclohexene-1-ethanol. Similarly, Me2CHCH:CH2 gave 37% Me2C:CH(CH2)3OH and 28% CH2:CHCMe2CH2CH2OH. [on SciFinder...

Hydroxyäthylallene und andere Folgeprodukte aus Dihydrofuran-Derivaten (1975)

Schaub, Bruno, Schlosser, Manfred

Upon treatment with organolithium compds., 2-alkyl-4,5-dihydrofurans underwent ring opening through b-elimination to give the corresponding 3,4-dien-1-ol. 3-Chloro-2-methyl-4,5-dihydrofuran gave...

Prescriptions and Ingredients for Controlled CC Bond Formation (1975)

alpha-Metallierte Enäther als "Masken" für Acyl-Anionen (1974)

Merits and drawbacks of known C-C linking procedures, such as condensation, addn., and isomerization reactions, are outlined. Two novel methods are discussed in more detail: the Cu-catalyzed...

Hartmann, Juergen, Staehle, Manfred, Schlosser, Manfred

H2C:CHCH2OR (R = tetrahydropyranyl) gave a mixt. of H2C:CHCHR1OH and R1CHCH2CHO after metalation and reaction with an electrophilic agent R1X, whereas metalation of MeCH:CHOR (R = tetrahydropyranyl)...

(Z)-Crotylalkoholate mit metalltragenden olefinischen Kohlenstoffatomen (1974)

Schlosser, Manfred, Hammer, Erwin

Dehydrobromination of threo-MeCHBrCHBrCH2OH gave (E)-2- and (E)-3-bromo-2-buten-1-ol, which with EtMeCHLi gave, resp., (E)-MeCH:CLiCH2OLi and (E)-MeCLi:CHCH2OLi; these with MeI or ethylene oxide gave...

Die Photofragmentierung eines Phosphor-Ylids (1974)

Duerr, Heinz, Barth, Dieter, Schlosser, Manfred

Short-wavelength irradn. of Ph3P+C-Me2 gave C6H6 and a resinous compd. Long-wavelength irradn. of Ph3P+C-Me2 gave mainly Ph3P and Me2C:CMe2 with some Me2CHCHMe2, MeCH:CH2, and, with Me2CHCHMe2 as...

Metallierung und Abwandlung funktionell substituierter Alkene (1974)

Hartmann, Juergen, Muthukrishnan, Ramamurthi, Schlosser, Manfred

1,4-Dienes, vinyl ethers, allyl ethers, allyl thio ethers, and propenethiolates were metalated by BuLi in the presence of an activator such as KOCMe3. Since the solvent, the counter-ion, or the temp....

Konfigurativ einheitliche Folgeprodukte aus Alkenylkalium-Zwischenstufen (1974)

Schlosser, Manfred, Hartmann, Juergen, David, Victor

Me groups adjacent to an olefinic double bond were metalated by KOCMe3 and BuLi without cis-trans isomerization. Thus, (E)-MeCH:-CHMe was metalated to give (E)-MeCH:CHCH2K (I) which reacted with...

Recipes and ingredients for controlled C-C linkages with organometallic reagents (1974)

Silberion-induzierte Ringöffnung von Chlorofluorocyclopropanen (1974)

A review with 37 refs. about C-C linkages with organometallic compds., esp. the Cu-catalyzed alkylation of Grignard reagents, giving satd. and unsatd. hydrocarbons optionally substituted by...

Le Van, Chau, Schlosser, Manfred

MeCR:CFCH2OH (R = Me, Pr, (CH2)3OAc) were prepd. in 53-60% yield by ring-cleavage of the cyclopropanes I with AgOAc-AgBF4 to give 50-64% MeCR:CFCH2OAc followed by hydrolysis. The isomeric acetates...

Verlaufen 1,3-Eliminierungen konzertiert oder nicht ? (1974)

Schlosser, Manfred, Fouquet, Gerd

PrCHBrCH2CHPrR (R = Br, F, or I) were converted into 1,2-dipropylcyclopropane by various metallic or organometallic reducing agents. Normally, cyclization occurred in a stereoconvergent manner, i.e....

Chiralitätserhaltung bei der enthalogenierenden Cyclopropan-Bildung aus optisch aktivem 4,6-Dibromnonan (1974)

Schlosser, Manfred, Fouquet, Gerd

Treatment of optically active (PrCHBr)2CH2 with Li-Hg or biphenyl-Li gave 46:54 or 59:51, resp., cis- and trans-1,2-dipropylcyclopropane (I). The original (R,R)-configuration at both chiral centers...

Improved Carbon-Carbon Linking by Controlled Copper Catalysis (1974)

Fouquet, Gerd, Schlosser, Manfred

Treatment of RO3SC6H4Me-4 with R1MgBr in THF over Li2CuCl4 at -78 Deg with slowly raising the temp. to room temp. gave, in good yields, the derivs. RR1 (R = e.g. Et, Ph, cyclohexyl, or octyl; R1 =...

Presciptions and Ingredients for Controlled CC Bond Formation with Organometallic Reagents (1974)

Metallbindungsphänomene : Alkoholat-Aggregate als unmittelbare Teilnehmer an Eliminierungsreaktionen (1973)

Schlosser, Manfred, Jan, Gerald, Byrne, Edeline, Sicher, Jiri

Kinetic data were obtained for the dehydrohalogenation in C6H6 and PhMe of vic-dihaloalkanes and vic-dihalocycloalkanes in the presence of KOCMe3. The mechanism involved oligomeric alc. aggregates...

Transmetalation and double metal exchange. Convenient way to organolithium compounds of the benzyl and allyl type (1973)

Schlosser, Manfred, Hartmann, Juergen

Treating PhMe with BuLi in the presence of KOCMe3 gave PhCH2K, which on LiBr treatment was converted into 85% PhCH2Li, characterized with Me3SiCl as PhCH2SiMe3. Similarly, at -20 Deg H2C:CMe2 gave...

Structure and Reactivity of Polar Organometallic Compounds; an Introduction to the Chemistry of Organic Alkali Metal and Alkaline Earth Metal Compounds (Organic Chemistry in Monographs, Vol. 14) (1973)

Chlorfluorcyclopropane durch Zweiphasenreaktion (1973)

Le Van, Chau, Schlosser, Manfred

Cl2CHF reacted with olefins in a 2-phase system to give 15-74% 1-chloro-1-fluorocyclopropanes. [on SciFinder (R)]

Attractive Interactions in E2 Reactions : the Origin of the syn-anti Duality and the Divergent Stereoselectivity of the Two Competing Pathways (1973)

Zàvada, J., Pànkovà, M., Svoboda, M., Schlosser, Manfred

3-Chlor-4,5-dihydrofuran : ein nützlicher Synthesebaustein (1973)

Schlosser, Manfred, Schaub, Bruno, Spahic, Bojana, Sleiter, G.

SCOOPY-Reaktionen : Die Regioselektivität der Alkenol-Synthese (1972)

Schlosser, Manfred, Coffinet, Danielle

Ph3P+CH2R (R = H, Me) reacted with aldehydes R1CHO (R1 = n-C5H11, Me2PrC, Ph) in the presence of BuLi and HCHO to give primary alkenols R1CH:CRCH2OH; ketones R2R3CO [R2, R3 = Me, Ph or (CH2)4,...

Optisch aktives Dipropylcyclopropan durch enthalogenierende Cyclisierung von optisch aktivem 4,6-Dibromnonan (1972)

Schlosser, Manfred, Fouquet, Gerd

Optically active trans-dipropylcyclopropane (I) and its optically inactive cis isomer (II) were prepd. from nonane-4,6-dione by redn. with NaBH4, esterification of the di-Li salt with phthalic...

Herstellung von Olefinen durch Abspaltungsreaktionen : Einleitung (1972)

Herstellung von Olefinen durch Abspaltungsreaktionen : Abspaltung von Halogenwasserstoff (1972)

Herstellung von Olefinen durch Abspaltungsreaktionen : Abspaltung von Halogen aus Dihalogen-alkenen (1972)

Herstellung von Olefinen durch Abspaltungsreaktionen : Gemeinsame Abspaltung von Halogen und einer Sauerstoff-Gruppe (1972)

Preferred syn-elimination from trans-1,2-dichloro- and trans-1,2-dibromocyclodecane (1971)

Sicher, Jiri, Jan, Gerald, Schlosser, Manfred

syn-Coplanar cleavage of hydrogen halide, esp. the syn -> trans process, was favored in the dehydrohalogenation of trans-1,2-dichlorocyclodecane and trans-1,2-dibromocyclodecane, and the anti...

Die Einwirkung von Metall-Alkoholaten auf cis- und trans-Styrylchlorid (1971)

Reaktionen zwischen Vinylfluoriden und Lithiumorganylen (1971)

The alcoholate-induced dehydrochlorination of styryl chloride possibly occurs by the 3 different competing mechanisms: E2, E1cb, and E1cb-HBA an E1cb modification. These conclusions were confirmed by...

Schlosser, Manfred, Zimmermann, Manfred

Reaction of cis- and trans-PhCH:CHF with RLi (R = Bu, Me, Ph, or PhCH2) gave stereoselectively cis- and trans-PhCH:CHR, with retention of configuration by substitution and PhC.tplbond.CH by...

SCOOPY-Reaktionen : Stereoselektivität der Allylalkohol-Synthese via Betain-Ylide (1971)

Schlosser, Manfred, Coffinet, D.

The stereoselectivity of the SCOOPY reaction, in which allyl alc. derivs. are prepd. by reaction of betaine ylides with carbonyl compds., was investigated by the synthesis of 1-hydroxy-2-octene (I),...

Fluorchlorcyclopropane : ihre Darstellung und Abwandlung (1971)

Schlosser, Manfred, Heinz, Gerhard, Le Van, Chau

Reaction of olefins with CHCl2F and BuLi gave stereospecifically the cis and trans isomers of 2-R1, 2-R3, 3-R2, 3-R4 = tetrasubstituted 1-chloro-1-fluorocyclopropanes (I) (R1 = H, Me; R2 = H, Me, Pr;...

Monofluorocarben (1971)

Schlosser, Manfred, Heinz, Gerhard

Reaction of olefins with CHFBr2 and BuLi gave stereospecific cis and trans isomers of alkyl-substituted fluorocyclopropanes (I, R, R1, R2, R3 = H, Me, Pr, C5H11). The addn. was also stereoselective...

Alkyl/halogen substitution in carbenes (carbenoids): a route to new cyclopropane derivatives (1971)

Schlosser, Manfred, Le, Van Chau

7-Halo-7-methylnorcaranes (I) and 7,7-dimethylnorcarane (II) are formed via replacement of halogen by Me during the reaction of cyclohexene (III) with carbenes (carbenoids) and MeLi. Thus, III is...

Stereoselectivity of a,a'-diastereogenic reactions (1971)

Mechanismen nucleophiler Austauschreaktionen : Ligandenaustausch an Phosphoranen und Stiboranen (1971)

A review of kinetic control in the diastereogenic formation of C-C bonds, Diels-Alder reactions, [2 + 2] cyclodimerization of olefins, syn preference in the formation of cyclopropanes from olefins...

Schlosser, Manfred, Kadibelban, Taufik, Steinhoff, Guenter

Pentacovalent P and Sb compds., e.g. pentaphenyl-phosphoranes, phenyldi(biphenylylene)phosphoranes, and alkyl, phenyl, or mixed phenylalkylstiboranes, readily underwent nucleophilic ligand exchange...

a-Substitution plus carbonyl olefination via b-oxido phosphorus ylids (S.C.O.O.P.Y.-reactions) scope and stereoselectivity (1971)

Schlosser, Manfred, Christmann, Karl F., Piskala, Alois, Coffinet, D.

Consecutive treatment of HOCH2CH2P+Ph3 Br- with BuLi, BzH, BuLi, and H2O afforded trans-PhCH:CHCH2OH in 95% isomeric purity and PhCH(OH)CH:CH2. The stereospecificity of the S.C.O.O.P.Y.-reactions...

La stéréosélectivité des réactions alpha,alpha'-diastéréogènes (1971)

Ist der Ylid-Kohlenstoff in Triphenylphosphonio-alkyliden planar oder pyramidal konfiguriert ? (1971)

Piskala, Alois, Fouquet, G., Zimmermann, M., Schlosser, Manfred

Stereochemistry of the Wittig reaction (1970)

Stereochemistry of olefination by phosphorus ylides (1970)

A review, with 91 refs., of stereoselectivity in reactions of stable and reactive ylids, and the application of stereoselective carbonyl olefinations. [on SciFinder (R)]

Die Beeinflußbarkeit der syn-Stereoselektivität bei Carben-Additionen an Olefine (1970)

A review, with 6 refs., of the prepn. of olefins from phosphonium ylides and carbonyl compds. and from phosphonium ylides, carbonyl compds., org. Li compds., and reactive halogen compds., such as...

Schlosser, Manfred, Heinz, Gerhard

The syn-anti ratio of 7-(R-substituted)-norcaranes (I, R = Ph. F, Cl) formed in the cycloaddn. of cyclohexene (II) with PhCH2F, PhCH2Cl, PhCHBrF, PhCHBr2, FCHBr2, ClCHBr2, or CH2Cl and BuLi in...

beta-Oxido-Ylide (Betain-Ylide) in salzfreiem und salzhaltigem Medium (1970)

Schlosser, Manfred, Christmann, Karl F., Piskala, Alois

Reaction of Ph3P+C-HR with R1CHO at -78 Deg yielded Ph3P+CHRCHR1O- (I). Subsequent addn. of BuLi gave Ph3P+C-RCHR1O- Li+ (II). Reaction of II with HCl and hydrolysis with tert-BuOK gave .apprx.80%...

Eine Methode zur Epimerisierung von 1,2-Diolen (1970)

Schlosser, Manfred, Weiss, Peter

Diols, meso- and dl-PrCH(OH)CH(OH)Pr, cis- and trans-1,2-cyclohexanediol, 9,10,-cis-dihydroxy-cis,trans-1,5-cyclododecadiene, trans-7,8-dihydroxybicyclo[4.2.0]octane, and I, are epimerized by heating...

Nor-squalen (1970)

Schlosser, Manfred, Piskala, Alois

Wittig reactions of the ylide (Ph3P+CH-)2CH2 (I) with aliphatic aldehydes and ketones are described. A soln. of I in THF prepd. from (Ph3P+CH2)2CH2.2Br- was treated with an equimolar amt. of...

Fluor-olefine durch Fluormethylenierung von Carbonylverbindungen (1969)

Schlosser, Manfred, Zimmermann, Manfred

Stirred 10.25 g ClO3F in 300 ml MePh at -70 Deg, under N, was treated with 160 ml 0.41M triphenylphosphonium methylide to give 98% [Ph3P+CH2F]ClO3- (I), m. 131-4 Deg (CH2Cl2-AcOH-EtOAc). Satd. 1...

Carbonyl olefination with a-substitution (1969)

Schlosser, Manfred, Christmann, Karl F.

Deprotonated phosphorus betaines react with D, alkyl, or halogen donors to form a-substituted derivs. which decomp. either spontaneously or after \"activation\" to give Ph3PO and olefins with the...

The carbene/carbenoid problem (1969)

Schlosser, Manfred, Heinz, Gerhard

PhCHXX1 (I where X = H, X1 = F or Cl; X = X1 = Br; or X = B r, X1 = F) were treated with BuLi and cyclohexene (II) to give syn-7 - phenylnorcarane (III) and its anti isomer (IV). The III/IV ratio was...

Die Fluorolyse metallorganischer Bindungen durch Perchlorylfluorid (1969)

Schlosser, Manfred, Heinz, G.

La stéréochimie de l'oléfination par les ylures du phosphore (1969)

Fluoroorganic compounds and their importance in cancer research (1968)

Monofluorocarbene and its syn-anti selectivity (1968)

Review with 19 refs. The synthesis of compds. such as fluorobenzene and fluorocholesterol and use of these as antimetabolites are considered. [on SciFinder (R)]

Schlosser, Manfred, Heinz, G.

syn-Substituted cyclopropanes (syn-I) (R, R1, and X are above the plane) and anti-I (X is below the plane) are prepd. from R1R3C:CRR2 and :CHF (from Br2CHF and BuLi). syn- and anti-I(X = Cl) are also...

Organosodium and Organopotassium Compounds (1968)

Der Einfluß von Stereochemie und Substituenten auf die Reaktivität von Vinylhalogeniden (1967)

alpha-Chlor-cis-und alpha-Chlor-trans-styryllithium (1967)

RCH:CHCl (R = Ph, o-, m-, and p-MeC6H4, 2,4,6-Me3C6H2, PhCH2, PhCH:CH, PhC.tplbond.C, a-furyl, etc.) reacted with PhLi to give RC.tplbond.CLi with the intermediate formation of RCH:CLiCl. cis-...

Mechanismus der Reaktion zwischen Styrylchlorid und Lithiumorganylen (1967)

cis- and trans-PhCH:CLiCl were stable at low temps. The compd. treated with PhLi eliminated HCl by an E2cB mechanism. [on SciFinder (R)]

Olefination with phosphorus ylides. I. Mechanism and stereochemistry of the Wittig reaction (1967)

cis-and trans-PhCH:- CHCl reacted with PhLi by an E2cB mechanism. The slow, ratedetg. formation of PhCH:CLiCl was followed by a fast HCl elimination with the formation of PhC.tplbond.CLi. [on...

Schlosser, Manfred, Christmann, Karl F.

Unstabilized P ylides and their betaines added Li salts, losing most of their reactivity, and were reactivated with tert-BuOK, making thus possible the retardation or the acceleration of the Wittig...

Preparation of fluorocyclopropanes by reductive dechlorination of chlorofluorocyclopropanes (1967)

Schlosser, Manfred, Heinz, G.

Treatment of Cl2CF2 with a base in the presence of an olefin gave chlorofluorocyclopropanes (I), which were distd. in a spinning band column and taken up in tetrahydrofuran (THF). This soln. was...

Notiz über die Darstellung reiner Lithiumaryle (1967)

Zur Aktivierung lithiumorganischer Reagenzien (1967)

The halogen metal interconversion between BuLi and PhI yields cryst. PhLi of about 99.8% purity, if certain reaction conditions are applied. Similarly, other pure aryllithium compds. have been prepd....

Natrium- and kalium-organische Verbindungen (1967)

K alkoxides enhance the reactivity of organolithium compds. even more than polar ethers. While in 1,2-dimethoxyethane PhLi can lithiate triarylmethanes, diarylmethanes, and furan; BuLi will, in the...

Mechanismus und Stereochemie der Wittig-Reaktion (1967)

Schlosser, Manfred, Christmann, K. F.

Nucleophilic ligand exchange by phosphoranes (1966)

Schlosser, Manfred, Kadibelban, Taufik, Steinhoff, G.

The org. groups of pentaorganylphosphorus compds. were found to undergo nucleophilic exchange with organolithium reagents. If an ethereal soln. of pentaphenylphosphorus is treated at room temp. with,...

(Mechanismus der Dehydrochlorierung von Vinylchloriden mit lithiumorganischen Reagenzien und Stereochemie der Carbonyl-olefinierung mit Phosphor-Yliden). (1966)

Stereoselective Wittig Reactions (1965)

(Lag nicht vor)

Eine Methode zur Darstellung selektiv deuterierter Verbindungen (1964)

Organosodium and Organopotassium Compounds : Preparation and Synthetic Applications (1964)

H atoms in the a-position to a quadricovalent P atom could be exchanged by D with D2O under mild alk. conditions. The phosphonium salts, which can be readily deuterated under these conditions, served...

Organosodium and Organopotassium Compounds : Properties and Reactions (1964)

Über den Mechanismus der Chlorwasserstoff-Abspaltung asu Styrilchlorid (1964)

Schlosser, Manfred, Ladenberger, V.

Rearrangement and degradation of alpha-heterofunctional substituted phosphonium salts (1962)

Über die Herstellung von Vinyläthern, Vinylthioäthern und Vinylhalogeniden auf der Phosphylen-Basis (1961)

cf. CA 55, 23400c; Hellmann and Bader, CA 56, 11615h. Treatment of phosphonium salts of the type (Ph3PCH2X)OH(I, X = SMe; II, X = Cl; III, X = Br) with N aq. NaOH gave Ph3PO and MeX. With II and III...

Wittig, Georg, Schlosser, Manfred

cf. CA 55, 13345i. MeOCH2Ph3PCl (I), m. 201-2 Deg (decompn.) (CHCl3-AcOH), was prepd. (86%) from 0.19 mole Ph3P (II) and 0.2 mole ClCH2OMe in 120 ml. C6H6 (60 hrs. at 50 Deg); I borate analog m....

Abwandlung der Phosphylen-Methodik : über Phosphin-alkylene als olefinbildende Reagenzien (1961)

Wittig, Georg, Weigmann, Hans D., Schlosser, Manfred

cf. CA 50, 10030g. The stationary ligands on the P were varied in order to obtain an insight into the mechanism of the carbonyl-olefination with triphenylphosphylenes. The results demonstrated that...

Ergebnisse der Operation bei Mega-Ureter. (1961)

(Carbonyl-Olefinierungen mit Phosphin-alkylenen). (1960)

Leipzig, Med. F., Diss. v. 25. Okt. 1961 (Nicht f. d. Aust.).

Der Einfluss verschieden konzentrierter Traubenzuckerlösungen auf die menschliche Haut. (1937)

Heidelberg, Naturwiss.-math. F., Diss. v. 25. Mai 1960 (Nicht f. d. Aust.).