Enantiocontrol in intramolecular cyclopropanation of diazoketones. Conformational control of metal carbene alignment

被引：26

作者：

Doyle, MP

Eismont, MY

Zhou, QL

机构：

[1] RUSSIAN ACAD SCI, ND ZELINSKII ORGAN CHEM INST, MOSCOW 117913, RUSSIA

[2] E CHINA UNIV SCI & TECHNOL, INST FINE CHEM, SHANGHAI 200237, PEOPLES R CHINA

来源：

RUSSIAN CHEMICAL BULLETIN | 1997年 / 46卷 / 05期

关键词：

diazo ketones; enantioselective intramolecular cyclopropanation; chiral dirhodium(II) carboxamidates; chiral copper semicorrins; chiral copper bisoxazolines; metal carbenes;

D O I：

10.1007/BF02496127

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Diazo ketones with gamma or delta double bonds undergo catalytic intramolecular cyclopropanation. These reactions occur with high enantiocontrol when catalyzed by copper semicorrins and bis-oxazolines, but low enantiocontrol characterizes reactions catalyzed by a broad selection of chiral dirhodium(II) carboxamidates. The reverse stereocontrol occurs for intramolecular cyclopropanation of allylic and homoallylic diazoacetates and diazoacetamides. This divergence is explained by conformational control of carbonyl alignment (syn or anti to the metal) of the metal carbene intermediate.

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页码：955 / 958

页数：4

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