Highly Enantioselective Synthesis of α,α-Dialkylmalonates by Phase-Transfer Catalytic Desynnmetrization

被引：50

作者：

Hong, Suckchang ^{[1
,2
]}

Lee, Jihye ^{[1
,2
]}

Kim, Minsik ^{[1
,2
]}

Park, Yohan ^{[3
]}

Park, Cheonhyoung ^{[1
,2
]}

Kim, Mi-hyun ^{[1
,2
]}

Jew, Sang-sup ^{[1
,2
]}

Park, Hyeung-geun ^{[1
,2
]}

机构：

[1] Seoul Natl Univ, Pharmaceut Sci Res Inst, Seoul 151742, South Korea

[2] Seoul Natl Univ, Coll Pharm, Seoul 151742, South Korea

[3] Inje Univ, Coll Pharm, Gimhae 621749, Gyeongnam, South Korea

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2011年 / 133卷 / 13期

基金：

新加坡国家研究基金会;

关键词：

ALPHA-AMINO-ACIDS; ORGANOCATALYTIC MICHAEL ADDITION; BETA-KETO-ESTERS; ASYMMETRIC ALKYLATION; STEREOSELECTIVE-SYNTHESIS; 1,3-DICARBONYL COMPOUNDS; ALLYLIC ALKYLATIONS; CONJUGATE ADDITION; CARBON CENTER; NITROALKENES;

D O I：

10.1021/ja110349a

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

A novel enantioselective synthetic method for the construction of a quaternary carbon center from malonates via phase-transfer catalytic (PTC) alkylation has been developed. The asymmetric alpha-alkylation of diphenylmethyl tertbutyl alpha-alkylmalonates with alkylating agents under phase-transfer catalysis conditions (aq 50% KOH, toluene, 0 degrees C) in the presence of (S,S)-3,4,5-trifluorophenyl-NAS bromide (8) as PTC catalyst afforded the corresponding alpha,alpha-dialkylmalonates in high chemical (up to 99%) and optical yields (up to 97% ee) which could be readily converted to versatile chiral intermediates. Notably, the direct double alpha-alkylations of diphenylmethyl tert-butyl malonate also provided the corresponding alpha,alpha-dialkylmalonates without loss of enantioselectivity. The synthetic potential of this method has been demonstrated by the preparation of alpha,alpha-dialkylamino acid and oxindole systems.

引用

页码：4924 / 4929

页数：6

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