A unique approach to metal-induced Bergman cyclization: Long-range enediyne activation by ligand-to-metal charge transfer

被引：29

作者：

Bhattacharyya, S ^{[1
]}

Pink, M ^{[1
]}

Baik, MH ^{[1
]}

Zaleski, JM ^{[1
]}

机构：

[1] Indiana Univ, Dept Chem, Bloomington, IN 47405 USA

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2005年 / 44卷 / 04期

关键词：

D O I：

10.1002/anie.200461825

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Dramatic differences are found in the temperatures at which Bergman cyclizations occur when MoIV-enedithiolate-enediyne complexes are used (see scheme; S: yellow, Mo: red), and this can be directly attributed to a long-range electronic polarization effect of the metal center. Ligand-to-metal charge transfer within the C2S4 substructure and differential charge repulsion in the transition state lead to a lowering of the barrier to cyclization.

引用

页码：592 / 595

页数：4

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