Synthesis and evaluation of a broad range of chiral sulfides for asymmetric sulfur ylide epoxidation of aldehydes

被引:32
作者
Aggarwal, VK
Angelaud, R
Bihan, D
Blackburn, P
Fieldhouse, R
Fonquerna, SJ
Ford, GD
Hynd, G
Jones, E
Jones, RVH
Jubault, P
Palmer, MJ
Ratcliffe, PD
Adams, H
机构
[1] Univ Sheffield, Dept Chem, Sheffield S3 7HF, S Yorkshire, England
[2] Univ Bristol, Sch Chem, Bristol BS8 1TS, Avon, England
[3] ZENECA Proc Technol Dept, Grangemouth FK3 8XG, Stirling, Scotland
来源
JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 1 | 2001年 / 20期
关键词
D O I
10.1039/b105416n
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
We have recently developed a catalytic, sulfur ylide mediated process for converting aldehydes into epoxides using benzaldehyde tosylhydrazone sodium salt which decomposes to generate phenyldiazomethane in situ. Although chiral 1,3-oxathianes gave good yields and excellent diastereo- and enantio-control when phenyldiazomethane was employed, only low yields were obtained when using the simplified procedure employing benzaldehyde tosylhydrazone sodium salt. Thus, a range of more robust chiral sulfides based on thianes, thiolanes, and 1,4-oxathianes were designed to achieve high yield and high enantioselectivity. The sulfides all possessed the following. features: conformationally locked cyclic sulfide in which only one of the two lone pairs was accessible (not relevant for C-2 symmetric substrates); ylide conformation and face selectivity was to be controlled through non-bonded steric interactions. Chirality was introduced from chiral pool materials (camphor, amino acids, lactic acid, limonene, carvone, glyceraldehyde); through enzyme mediated reduction/hydrolysis and through the use of chiral reagents (hydroboration). The sulfide catalysts were tested in the reaction between benzaldehyde tosylhydrazone salt and benzaldehyde to give traps-stilbene oxide. The range of chiral sulfide catalysts derived from camphor gave trans-stilbene oxide in generally-good yield (23-95%) and with moderate enantioselectivity (40-76% ee). The range of novel chiral thianes and 1,4-oxathianes gave traps-stilbene oxide again in generally good yield (9-92%) and with moderate enantioselectivity (20-77% ee). The range of C-2 symmetric chiral sulfide catalysts based on 5 and 6 membered rings gave traps-stilbene oxide in moderate yield (10-78%) and with variable enantioselectivity (8-87% ee). In none of the cases could high enantioselectivity and high yield be achieved simultaneously. Analysis of the results led us to the conclusion that the moderate enantioselectivity was a result of poor control in the ylide conformation and this led to the design of completely rigid [2.2.1] bicyclic sulfides which finally,gave high enantioselectivity and high, yield in the epoxidation process.
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收藏
页码:2604 / 2622
页数:19
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