DIASTEREOSELECTIVITY IN THE O-H INSERTION REACTIONS OF RHODIUM CARBENOIDS DERIVED FROM PHENYLDIAZOACETATES OF CHIRAL ALCOHOLS - PREPARATION OF ALPHA-HYDROXY AND ALPHA-ALKOXY ESTERS

被引：76

作者：

ALLER, E ^{[1
]}

BROWN, DS ^{[1
]}

COX, GG ^{[1
]}

MILLER, DJ ^{[1
]}

MOODY, CJ ^{[1
]}

机构：

[1] LOUGHBOROUGH UNIV TECHNOL,DEPT CHEM,LOUGHBOROUGH LE11 3TU,LEICS,ENGLAND

来源：

JOURNAL OF ORGANIC CHEMISTRY | 1995年 / 60卷 / 14期

关键词：

D O I：

10.1021/jo00119a023

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

A series of phenyldiazoacetates 3 derived from enantiomerically pure alcohols ((-)-borneol, (+)menthol, (-)-menthol, (-)-8-phenylmenthol, (-)-trans-2-phenylcyclohexanol, (+)-trans-2-phenyl-cyclohexanol, and (-)10-(dicyclohexylsulfamoyl)-D-isoborneol) were prepared from the corresponding alpha-keto esters 1 by way of the tosylhydrazones 2. Rhodium(II)-catalyzed decomposition of the diazoacetates 3 in the presence of water or alcohols resulted in carbenoid O-H insertion reactions to give the corresponding 2-hydroxy- or 2-alkoxyphenylacetates in good yield, but with varying degrees of diastereoselectivity. A range of rhodium(II) and other metal catalysts were investigated, with rhodium(II) acetate and rhodium(II) acetamide giving the best results. The stereochemistry of the major diastereomer was proved in most cases by independent synthesis from a mandelic acid derivative of known configuration. Possible mechanisms are discussed.

引用

页码：4449 / 4460

页数：12

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