Two types of intramolecular homolytic substitution reactions at group XIV atoms:: unusual radical 1,4-Sn shifts from Si to C and carbonylative SHi reaction at Si

被引：24

作者：

Studer, A

Amrein, S

Matsubara, H

Schiesser, CH

Doi, T

Kawamura, T

Fukuyama, T

Ryu, I

机构：

[1] Univ Marburg, Fachbereich Chem, D-35032 Marburg, Germany

[2] Univ Melbourne, Bio21 Inst Mol Sci & Biotechnol, Sch Chem, Parkville, Vic 3010, Australia

[3] Osaka Prefecture Univ, Fac Arts & Sci, Dept Chem, Osaka 5998531, Japan

来源：

CHEMICAL COMMUNICATIONS | 2003年 / 10期

关键词：

D O I：

10.1039/b301755a

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

4-[(Trimethylstannyl) diphenylsilyl] butanoyl radical, arising from the corresponding 3-(stannylsilyl) propyl radical and CO, undergoes an S(H)i reaction at Si with extrusion of trimethyltin radical to give silacyclopentanone. The parent 3-( stannylsilyl) propyl radical was also found to isomerize to (3-stannylpropyl) silyl radical via a 1,4-Sn shift from Si to C with a rate constant of 9.3 x 10(4) s(-1) at 80 degreesC. Ab initio and DFT MO calculations support a front-side attack mechanism.

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页码：1190 / 1191

页数：2

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