The addition of alkynes to a tetrasilyidisilene - Evidence for a biradical intermediate

被引：15

作者：

Gottschling, SE ^{[1
]}

Jennings, MC ^{[1
]}

Baines, KM ^{[1
]}

机构：

[1] Univ Western Ontario, Dept Chem, London, ON N6A 5B7, Canada

来源：

CANADIAN JOURNAL OF CHEMISTRY | 2005年 / 83卷 / 09期

关键词：

disilene; alkyne; cycloaddition; reaction mechanism; mechanistic probe;

D O I：

10.1139/v05-169

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The addition of two newly developed mechanistic probes, (trans,trans-2-methoxy-3-phenylcyclopropyl)ethyne (1) and (trans,trans-2-methoxy-1-methyl-3-phenylcyclopropyl)ethyne (2), to tetrakis(tert-butyldimethylsilyl)disilene (3) has been investigated. The addition of 1 to 3 gave [-[2-(cis-2-methoxy-3-phenylcyclopropylidene)vinyl]-1,1,2,2-tetrakis(tert-butyldimethylsilyl)disilane (5) as the major product; whereas addition of alkyne 2 to the disilene gave three stereoisomers of 1,1,2,2-tetrakis(tert-butyldimethylsilyl)-6-methoxy-5-methyl-7-phenyl-1,2-disilacyclohepta-3,4-diene (7-9) and 1, 1.2,2-tetrakis(tert-butyldimethylsilyl)-3-(trans,trans-2-methoxy-1-methyl-3-phenylcyclopropyl)- 1,2-disilacyclobut-3-ene (10) as the major products. The formation of cycloheptaallenes 7-9 provides convincing evidence that the addition of alkynes to tetrasilyldisilenes involves the formation of a biradical intermediate.

引用

页码：1568 / 1576

页数：9

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