ASYMMETRIC-SYNTHESIS USING N,N-DIALKYLNOREPHEDRINES AND PYRROLIDINYLMETHANOL DERIVATIVES AS CHIRAL CATALYSTS AND LIGANDS

被引:5
作者
SOAI, K
HAYASE, T
机构
[1] Department of Applied Chemistry, Faculty of Science, Science University of Tokyo
关键词
CHIRAL CATALYST; DIBUTYLNOREPHEDRINE; ENANTIOSELECTIVE SYNTHESIS; ASYMMETRIC SYNTHESIS; ASYMMETRIC AUTOCATALYST; SELF-REPLICATION; AUTO-MULTIPLICATION; ORGANOZINC REAGENT; REFORMATSKY REACTION; OPTICALLY ACTIVE ALCOHOL;
D O I
10.5059/yukigoseikyokaishi.53.138
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
A series of N,N-dialkylnorephedrines and pyrrolidinylmethanol derivatives are synthesized as chiral catalysts and as chiral ligands for the highly enantioselective 1,2- and conjugate additions of organozinc reagents to aldehydes, ketones, phosphinylimines and alpha,beta- unsaturated ketones. N,N-Dibutylnorephedrine (DBNE) and diphenyl (1-methylpyrrolidin-2-yl) methanol (DPMPM) are used as chiral catalysts in the enantioselective addition of dialkylzincs to aldehydes (up to 100% ee). Chiral thiophosphoramidate and N-benzyl-N-methylephedrinium halides are also enantioselective catalysts. Polystyrene and silica gel (and alumina) supported N-alkylnorephedrines with or without a spacer are used as heterogeneous chiral catalysts. Chiral compounds prepared include sec- alcohols, furylacohols, alkynlalcohols, allylalcohols, beta- hydroxynitrile, fluorine-containing alcohols, deuterated alcohols, gamma-hydroxyketones, pyridylalkylalcohols, diols, hydroxyaldehyde, gamma- and delta-hydroxyesters, gamma-butyro- and delta-valerolactones. Enantioselective Reformatsky reaction with aldehydes and ketones using DPMPM and N,N-diallylnorephedrine affords chiral beta-sec, and beta-t-hydroxyesters, respectively. Enantioselective alkylation of aldehydes using DBNE is applied to the synthesis of chiral alkylphthalides, (+)-lepicidin A, and a precursor of tacalcitol. Diastereodivergent alkylations of alpha or beta-chiral aldehydes are achieved by using the appropriate enantiomer of DBNE or DPMPM. Self-replication and auto-multiplication of chiral zinc alkoxides of pyridylalkylalcohols and diols as asymmetric autocatalysts is descrided. Enantioselective and/or diasteroselective alkylation of diphenylphosphinylimine affords chiral amine. Chiral nickel complex with DBNE catalyzes the enantioselective conjugate addition of dialkylzincs to alpha,beta-unsaturated ketones.
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页码:138 / 150
页数:13
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