STEREOSELECTIVE REDUCTIONS OF 2-KETO SULFOXIDES WITH HYDRIDES

被引：172

作者：

CARRENO, MC ^{[1
]}

RUANO, JLG ^{[1
]}

MARTIN, AM ^{[1
]}

PEDREGAL, C ^{[1
]}

RODRIGUEZ, JH ^{[1
]}

RUBIO, A ^{[1
]}

SANCHEZ, J ^{[1
]}

SOLLADIE, G ^{[1
]}

机构：

[1] ECOLE EUROPEENE HAUTES ETUD IND CHIM,UA 466,F-67008 STRASBOURG,FRANCE

来源：

JOURNAL OF ORGANIC CHEMISTRY | 1990年 / 55卷 / 07期

关键词：

D O I：

10.1021/jo00294a027

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

The results of reductions of some acyclic 2-keto sulfoxides (ArC(o)CH2S(o)R; Ar = Ph, 2-Py, 4-Py, and R = Me, p-Tol) and flexible and rigid 2-sulfmylcyclohexanone diastereomers with various metal hydrides are reported. The configurational assignment and conformational preferences of these substrates have been inferred from their NMR parameters. The high stereoselectivity observed in i-Bu2A1H reactions can be explained by assuming its association with the sulfinyl oxygen and intramolecular hydride transfer via chair-like transition states. In the presence of ZnCl2 the hydride transfer evidently takes place intermolecularly on the half-chair conformation adopted by the chelated species formed by 2-keto sulfoxides and ZnCl2. The reductions with LiAlH4 involve lithium chelates to which hydride is intramolecularly transferred from associated A1H4~ through the most stable transition state. In all cases, an important role of the stereoelectronic effects on the favored hydride approach is proposed. © 1990, American Chemical Society. All rights reserved.

引用

页码：2120 / 2128

页数：9

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