PI-CYCLIZATIONS OF ALPHA-METHOXYCARBONYL OXYCARBENIUM IONS - SYNTHESIS OF OXACYCLIC CARBOXYLIC ESTERS

被引：45

作者：

LOLKEMA, LDM ^{[1
]}

HIEMSTRA, H ^{[1
]}

SEMEYN, C ^{[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)85238-8

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Acid-mediated cyclization reactions are described of seven methyl 2-acetoxy-2-(3-alken-1-oxy)acetates with different chain substitution. The major product of the tin tetrachloride-induced cyclization reaction is in most cases a tetrahydropyran containing an equatorial carbomethoxy function at C2 and an axial chlorine atom at C4. The mechanism of its formation involves a net cis-addition of the intermediate alpha-ester oxycarbenium ion to the carbon-carbon double bond, most likely caused by a quasi axial orientation of the ester function in a chair-like transition state. The results are interpreted by invoking (1) the occurrence of a 2-oxonia-Cope rearrangement and (2) the participation of the ester function in the mechanism of cyclization by trapping the cyclic cationic intermediate. The cyclizations of two methyl 2-acetoxy-2-(4-alken-1-oxy)acetates and two methyl 2-acetoxy-2-(alkynoxy)acetates are also described .

引用

页码：7115 / 7128

页数：14

共 62 条

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