コンホーメーションの固定による高選択的不斉合成.キレート生成を利用する不斉的炭素-炭素結合形成反応

概要

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This article mostly describes a highly efficient method for asymmetric carbon-carbon bond forming reactions based on the strategy of fixing the conformation of the chiral moiety of the imines, prepared from carbonyl compounds and optically active α-amino acid esters, by chelation of appropriate metals with the imine nitrogen and the ester oxygen suitably situated. Two types of reactions, 1,4-addition reaction of Grignard reagents or diethyl malonate anion to α, β-unsaturated aldimines and alkylation of metalloenamines, have been explored. The present method has advantages in providing β-substituted aldehydes, α-substituted cyclic ketones, trans- and cis-α, β-disubstituted cycloalkanecarboxaldehydes in quite high enantiomeric purities, allowing easy preparation of imines as well as easy recovery of tert-leucine tert-butyl ester, an excellent chiral reagent, without any loss of optical purity for reuse. Some mechanistic explanations on the stereochemical courses of the reactions are presented. Asymmetric Diels-Alder reactions catalyzed by optically active alkoxyaluminium dichlorides are also described.
公益社団法人日本薬学会の論文
1982-12-25