Eva M. Brun

New conditions for the generation of dianions of carboxylic acids

Abstract Lithium carboxylic acid enediolates are generated efficiently using lithium amides prepared from thienyllithium or butyllithium and either diethylamine, piperazine, N,N′-dibenzylethylenediamine, N-benzylpiperazine or 1,3,3-trimethyl-6-azabicyclo[3.2.1]octane, even in catalytic amounts.

LITHIUM ENEDIOLATES AND DIENEDIOLATES OF CARBOXYLIC ACIDS IN SYNTHESIS : ALKYLATION WITH SECONDARY HALIDES

Abstract High yields in the alkylation of dianions of α,β-unsaturated carboxylic acids with secondary halides can be obtained despite elimination reactions occurring. α-Regioselectivity for the alkylation of but-2-enoic acids ( 1–4 ) is seldom obtained. Although double bond stereoselectivity is higher than 99% for γ-alkylated products, stereoselectivity is rather poor for most of the α-alkylated products.

Enantioselective α-alkylation of unsaturated carboxylic acids using a chiral lithium amide

Abstract The regio- and stereochemistry of the alkylation of dienediolates from unsaturated carboxylic acids with benzylic halides, which often results in mixtures of isomers, can be controlled by means of changes in the lithium amide, allowing the α-regioisomer to be obtained as the major diastereoisomer. In addition, when chiral amines are used, moderate enantiomeric excesses can be attained.

Enediolates and dienediolates of carboxylic acids in synthesis. Synthesis of β,γ-epoxyacids from α-chloroketones

Abstract Lithium dienolates of saturated or α,β-unsaturated acids react with α-chloroketones provide a convenient method for preparation of highly sustituted β,γ-epoxyacids. These highly reactive compounds lead in most cases to variable ammounts of the corresponding β-lactones and allylic alcohols.