VITAMIN B12S-PROMOTED MODEL REARRANGEMENT OF METHYLMALONATE TO SUCCINATE IS NOT A FREE-RADICAL REACTION

被引：21

作者：

CHOI, GY ^{[1
]}

CHOI, SC ^{[1
]}

GALAN, A ^{[1
]}

WILK, B ^{[1
]}

DOWD, P ^{[1
]}

机构：

[1] UNIV PITTSBURGH, DEPT CHEM, PITTSBURGH, PA 15260 USA

来源：

PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA | 1990年 / 87卷 / 08期

关键词：

Carbanion; Coenzyme B[!sub]12[!/sub; Pentenylmalonate; Radical trap; Tri-n-butyltin hydride;

D O I：

10.1073/pnas.87.8.3174

中图分类号：

O [数理科学和化学]; P [天文学、地球科学]; Q [生物科学]; N [自然科学总论];

学科分类号：

07 ; 0710 ; 09 ;

摘要：

To probe for free radical intermediates in the model methylmalonate to succinate rearrangements promoted by vitamin B12s, a model series with a pentenyl side chain radical trap has been devised. The control free radical, generated by tri-n-butyltin hydride treatment of bromomethylpentenylmalonate thioester, undergoes rapid cyclization to the six-membered ring, and, as anticipated, no succinate rearrangement product is detected. By contrast when the bromide is treated with vitamin B12s, little cyclized product is observed; the major product is the pentenyl succinate. This result demonstrates that the latter rearrangement does not follow a free radical pathway.

引用

页码：3174 / 3176

页数：3

共 21 条

[1] REGIO-SELECTIVITY AND STEREO-SELECTIVITY OF ALKENYL RADICAL RING-CLOSURE - A THEORETICAL-STUDY [J].