Unequivocal SRN1 route of vinyl halides with a multitude of competing pathways:: Reactivity and structure of the vinyl radical intermediate

被引：54

作者：

Galli, C

Rappoport, Z

机构：

[1] Univ Roma La Sapienza, Dipartimento Chim, I-00185 Rome, Italy

[2] Univ Roma La Sapienza, Ctr CNR Meccanismi Reaz, I-00185 Rome, Italy

[3] Hebrew Univ Jerusalem, Dept Organ Chem, IL-91904 Jerusalem, Israel

[4] Hebrew Univ Jerusalem, Minerva Ctr Computat Quantum Chem, IL-91904 Jerusalem, Israel

来源：

ACCOUNTS OF CHEMICAL RESEARCH | 2003年 / 36卷 / 08期

关键词：

D O I：

10.1021/ar030028q

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Unambiguous examples of the vinylic S(RN)1 reaction initiated by a single-electron transfer from an electron-donor anion (Y-) to a suitable VyX substrate, and proceeding through a vinyl radical (Vy.) intermediate, are described. Competition by alternative substitution routes is extensive, but through a systematic modification of the structure of the substrate, unequivocal examples of the vinylic S(RN)1 route are documented. The geometry of the Vy. and kinetic parameters for H-abstraction and coupling with Y- are reported.

引用

页码：580 / 587

页数：8

共 63 条

[1] PHOTOSTIMULATED REACTION OF DIPHENYLARSENIDE AND DIPHENYLSTIBIDE IONS WITH HALOAROMATIC COMPOUNDS BY THE SRN1 MECHANISM - ELECTRON-TRANSFER VS BOND BREAKING OF THE RADICAL-ANION INTERMEDIATE [J].