Viscosity-control led, product-selective rearrangement of the cyclopentane-1,3-diyl radical cation derived from an annelated housane by electron transfer: A case of Curtin-Hammett behavior

被引：7

作者：

Adam, W

Librera, C

Trofimov, AV

机构：

[1] Univ Wurzburg, Inst Organ Chem, D-97074 Wurzburg, Germany

[2] Russian Acad Sci, Inst Biochem Phys, Moscow 117977, Russia

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2002年 / 124卷 / 40期

关键词：

D O I：

10.1021/ja026057y

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The fractional-power viscosity dependence of the product ratio [2]/[3] similar to eta(a3 a2) manifests the different free-volume requirements for the methylene (k(3) similar to eta(a3)) versus methyl (k(2) similar to eta(a2)) migrations. The syn/anti-conformational changes (k(1), k(-1)) in the radical cation 1(.+) proceed faster than the structural transformations (k(2), k(3)), which constitutes the first Curtin-Hammett case in radical-cation rearrangements.

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页码：11936 / 11939

页数：4

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