STUDIES ON THE ROLE OF THE 2-OXONIA COPE REARRANGEMENT IN PI-CYCLIZATIONS OF ALPHA-METHOXYCARBONYL OXYCARBENIUM IONS

被引：47

作者：

LOLKEMA, LDM ^{[1
]}

SEMEYN, C ^{[1
]}

ASHEK, L ^{[1
]}

HIEMSTRA, H ^{[1
]}

SPECKAMP, WN ^{[1
]}

机构：

[1] UNIV AMSTERDAM,ORGAN CHEM LAB,1018 WS AMSTERDAM,NETHERLANDS

来源：

TETRAHEDRON | 1994年 / 50卷 / 24期

关键词：

D O I：

10.1016/S0040-4020(01)85239-X

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

The 2-oxonia Cope rearrangement is shown to play an important role in Lewis acid-induced R-cyclization reactions of a variety of methyl 2-acetoxy-2-(3-alken-I-oxy)acetates to 5- and 6-membered ring ethers. The influence of this [3,3]-sigmatropic rearrangement on the regio- and stereochemical outcome of the cyclization is evaluated by studying three types of substrates, namely (1) four chain-substituted precursors, (2) three silicon-substituted precursors (allyl- and vinylsilanes) and (3) two enantiopure precursors. Controlling factors are the nature of the ri-nucleophile and the substitution pattern of the oxycarbenium ton intermediate. The absolute stereochemistry is retained in the cyclization of the enantiopure substrates.

引用

页码：7129 / 7140

页数：12

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