ASYMMETRIC INDUCTION IN THE THIO-CLAISEN REARRANGEMENT - CREATION OF 3 CONTIGUOUS STEREOGENIC CENTERS FROM ALPHA-HYDROXY KETENE DITHIOACETALS

被引：15
作者：
BESLIN, P
PERRIO, S
机构：
[1] Laboratoire de Chimie des Composés Thio-organiques (Associé au CNRS), ISMRA, Université de CAEN, 14050 Caen, 6, Boulevard du Maréchal Juin
来源：
TETRAHEDRON | 1992年 / 48卷 / 20期
关键词：
D O I：
10.1016/S0040-4020(01)92192-1
中图分类号：
O62 [有机化学];
学科分类号：
070303 ; 081704 ;
摘要：
Syn beta-hydroxy gamma-methyl dithioesters were deprotonated with two equivalents of LDA. A subsequent S-alkylation of the resulting dianions yielded alpha-hydroxy S-allyl ketene dithioacetals. A single isomer was observed, arising from a selective cis deprotonation. These dithioacetals underwent a rapid and highly diastereoselective thio-Claisen rearrangement at an ambient temperature. Syn-syn alpha-allyl beta-hydroxy gamma-methyl dithioesters were mainly formed. The syn-syn/anti-syn ratios ranged from 85:15 to 99:1. The selectivity observed originates from asymmetric: induction with a noteworthy stereoelectronic effect of the hydroxyl group. Configurations were assigned by a spectroscopic method using previously reported C-13 NMR rules and then confirmed by a syn-syn diastereoselective aldol reaction. This novel and efficient method for the creation of frameworks with three contiguous stereogenic centres, involves two diastereoselective steps: an aldol reaction followed by a thio-Claisen rearrangement.
引用
收藏
页码：4135 / 4146
页数：12
相关论文
共 85 条
[1]  
[Anonymous], 1965, CONFORMATIONAL ANAL
[2]   RECENT ADVANCES IN ASYMMETRIC-SYNTHESIS .2. [J].
APSIMON, JW ;
COLLIER, TL .
TETRAHEDRON, 1986, 42 (19) :5157-5254
[3]  
BARTLETT PA, 1980, TETRAHEDRON, V36, P2
[4]  
BEINER JM, 1972, CR ACAD SCI C CHIM, V274, P642
[5]  
BENNETT GB, 1977, SYNTHESIS-STUTTGART, P589
[6]  
BERRADA S, 1985, B SOC CHIM FR, P881
[7]   SIMPLE, DIASTEREOFACIAL SELECTIVITY OF PROPANEDITHIOIC ACID ALDOLIZATION-REACTIONS [J].
BESLIN, P ;
HOUTTEVILLE, MC .
TETRAHEDRON, 1989, 45 (14) :4445-4456
[8]   DIASTEREOCONTROL OF THIO-CLAISEN REARRANGEMENT INDUCED BY AN ADJACENT HYDROXY-SUBSTITUTED CHIRAL CENTER [J].
BESLIN, P ;
PERRIO, S .
JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1989, (07) :414-416
[9]   STEREOCONTROLLED FORMATION OF 2 CONTIGUOUS CHIRAL CENTERS BY THIO-CLAISEN REARRANGEMENT OF S-ALLYLATED ALPHA-HYDROXYKETENE DITHIOACETALS [J].
BESLIN, P ;
PERRIO, S .
TETRAHEDRON, 1991, 47 (32) :6275-6286
[10]   CIS-SELECTIVITY OF THE KINETIC DEPROTONATION OF DITHIOPROPANOATES [J].
BESLIN, P ;
METZNER, P ;
VALLEE, Y ;
VIALLE, J .
TETRAHEDRON LETTERS, 1983, 24 (34) :3617-3620
123456789