What is the stabilizing interaction with nucleophilic solvents in the transition state for solvolysis of tertiary derivatives: Nucleophilic solvent participation or nucleophilic solvation?

被引：55

作者：

Richard, JP ^{[1
]}

Toteva, MM ^{[1
]}

Amyes, TL ^{[1
]}

机构：

[1] SUNY Buffalo, Dept Chem, Buffalo, NY 14260 USA

来源：

ORGANIC LETTERS | 2001年 / 3卷 / 14期

关键词：

D O I：

10.1021/ol016103j

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

[GRAPHICS] We propose that controversy concerning the mechanism for solvolysis at tertiary carbon is semantic and can be avoided by making a clear distinction between (1) nucleophilic solvent participation, which is stabilization of the transition state for concerted solvolysis by formation of a partial covalent bond to the solvent nucleophile, and (2) nucleophilic solvation, which is stabilization of the transition state for stepwise solvolysis through carbocation or ion pair intermediates by charge-dipole interactions with nucleophilic solvents,

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页码：2225 / 2228

页数：4

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