STEREOSPECIFIC AMINATION BY DYNAMIC KINETIC RESOLUTION UTILIZING 2-OXOIMIDAZOLIDINE-4-CARBOXYLATE AS A NOVEL CHIRAL AUXILIARY

被引:54
作者
KUBOTA, H
KUBO, A
TAKAHASHI, M
SHIMIZU, R
DATE, T
OKAMURA, K
NUNAMI, K
机构
[1] TANABE SEIYAKU CO LTD,APPL BIOCHEM RES LAB,YODOGAWA KU,OSAKA 532,JAPAN
[2] TANABE SEIYAKU CO LTD,ORGAN RES LAB,TODA,SAITAMA 335,JAPAN
关键词
D O I
10.1021/jo00126a029
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
A novel type of stereospecific amination by dynamic kinetic resolution using (4S)-2-oxoimidazolidine-4-carboxylate (1) as a chiral auxiliary was developed. A reaction of a diastereomeric mixture of (4S)-3-[(2RS)-2-bromoacyl]-2-oxoimidazolidine-4-carboxylates 4 with an amine in the presence of a base in HMPA predominantly afforded (4S)-3-[(2R)-2-(alkylamino)acyl]-2-oxoimidazolidine-4-carboxylates (S,R)-7 in good yields. The reaction proceeded by stereospecific S(N)2 type amination incorporated with rapid interconversion between the substrates (S,S)-4 and (S,R)-4. Mechanistic study suggested that the unique stereoselectivity was induced through the interaction between an amine and the ester group of (S,S)-4 in the transition state. The chiral auxiliary was easily removed with alkoxide anion to afford the alpha-amino acid synthon in good yields.
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页码:6776 / 6784
页数:9
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