Which is more likely in trichodiene biosynthesis: Hydride or proton transfer?

被引：67

作者：

Hong, Young J. ^{[1
]}

Tantillo, Dean J. ^{[1
]}

机构：

[1] Univ Calif Davis, Dept Chem, Davis, CA 95616 USA

来源：

ORGANIC LETTERS | 2006年 / 8卷 / 20期

关键词：

D O I：

10.1021/ol061884f

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

[GRAPHICS] The mechanisms proposed for enzyme-catalyzed formation of the sesquiterpene natural product trichodiene consistently include a step involving a 1,4-hydride transfer. Using quantum chemical methods (B3LYP/6-31+G(d, p) and mPW1PW91/6-31+G(d, p)), we discovered two alternative pathways for transformation of the intermediate bisabolyl cation to the cuprenyl cation, one of which-a proton-transfer pathway-appears to be much more energetically favorable (by more than 10 kcal/mol) than the hydride transfer pathways usually proposed.

引用

页码：4601 / 4604

页数：4

共 23 条

[21] Role of arginine-304 in the diphosphate-triggered active site closure mechanism of trichodiene synthase [J].