GAMMA-SILICON STABILIZATION OF CARBONIUM-IONS IN SOLVOLYSIS .4. SOLVOLYSIS OF CIS-3-(TRIMETHYLSILYL)CYCLOHEXYL AND TRANS-3-(TRIMETHYLSILYL)CYCLOHEXYL AND CIS-3-TERT-BUTYLCYCLOHEXYL PARA-BROMOBENZENESULFONATES

被引：31

作者：

SHINER, VJ ^{[1
]}

ENSINGER, MW ^{[1
]}

KRIZ, GS ^{[1
]}

HALLEY, KA ^{[1
]}

机构：

[1] WESTERN WASHINGTON STATE UNIV,DEPT CHEM,BELLINGHAM,WA 98225

来源：

JOURNAL OF ORGANIC CHEMISTRY | 1990年 / 55卷 / 02期

关键词：

D O I：

10.1021/jo00289a047

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

The solvolyses of cis- and trans-3-(trimethylsilyl)cyclohexyl and -3-tert-butylcyclohexyl p-bromobenzenesulfonates (1–4) have been examined in several ethanol- and trifluoroethanol-water solvent mixtures. The a- and β-deuterium kinetic isotope effects have been determined, and the products have been identified. The cis-silyl compound (1) solvolyzes with participation by bridging across the ring between the γ-carbon and the reaction center, promoted by the γ-trimethylsilyl group. Products of the solvolysis are mainly those of substitution with retention of configuration, but a significant fraction of bicyclo[3.1.0Thexane is also formed. The trans-silyl compound (2) undergoes rate-determining ionization without significant acceleration by the trimethylsilyl group but with substantial participation by the β-hydrogens. The solvolysis products are 3- and 4-(trimethylsilyl)cyclohexenes formed by 1,2-elimination and cyclohexene formed by Wagner-Meerwein rearrangement and subsequent loss of the trimethylsilyl group. The solvolyses of the carbon analogue compounds (3 and 4) involve rate-determining ionization to form an intimate ion pair, followed by elimination of β-hydrogens or reaction with nucleophile. 1,2-Elimination is the principal product-forming process. © 1990, American Chemical Society. All rights reserved.

引用

页码：653 / 661

页数：9

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