Solvolysis of chiral cyclohexylidenemethyl triflate. Evidence against a primary vinyl cation intermediate

被引：6

作者：

Fujita, M ^{[1
]}

Yamamoto, A ^{[1
]}

Sugimura, T ^{[1
]}

Okuyama, T ^{[1
]}

机构：

[1] Himeji Inst Technol, Fac Sci, Kamigori, Hyogo 6781297, Japan

来源：

JOURNAL OF PHYSICAL ORGANIC CHEMISTRY | 2002年 / 15卷 / 08期

关键词：

vinyl triflate; vinyl cation; solvolysis; vinylic S(N)2 reaction; sigma-bond participation; rearrangement; chirality probe approach;

D O I：

10.1002/poc.485

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Solvolysis of (R)-4-methylcyclohexylidenemethyl triflate (6) was examined at 140degreesC in various aqueous methanol and some other alcoholic solvents. The main product was (R)-4-methylcycloheptanone that maintains the stereochemical purity of 6, with accompanying 4-methylcyclohexanecarbaldehyde. In the presence of bromide ion, the bromide substitution product was also obtained, mostly with inversion of configuration. It is concluded that the solvolysis does not involve the formation of the primary vinyl cation but proceeds via a-bond participation to form the rearranged cycloheptenyl cation as an intermediate. Copyright (C) 2002 John Wiley Sons, Ltd.

引用

页码：550 / 555

页数：6

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