Computationally Designed and Experimentally Confirmed Diastereoselective Rhodium-Catalyzed Pauson-Khand Reaction at Room Temperature

被引：38

作者：

Baik, Mu-Hyun ^{[1
]}

Mazumder, Shivnath ^{[1
]}

Ricci, Paolo ^{[2
]}

Sawyer, James R. ^{[1
]}

Song, Ye-Geun ^{[1
]}

Wang, Huijun ^{[1
]}

Evans, P. Andrew ^{[2
]}

机构：

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

[2] Univ Liverpool, Dept Chem, Liverpool L69 7ZD, Merseyside, England

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2011年 / 133卷 / 20期

关键词：

MECHANISM; DENSITY; VINYLCYCLOPROPANES; CYCLOADDITION; CO;

D O I：

10.1021/ja107895g

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The computational analysis of the rhodium-catalyzed Pauson-Khand reaction indicates that the key transition state is highly charge-polarized, wherein different diastereoisomers have distinctively different charge polarization patterns. Experimental studies demonstrate that chloro-enynes provide the optimal sigma-electron-withdrawing group to promote polarization and thereby reduce the activation barrier to provide a highly diastereoselective reaction at room temperature.

引用

页码：7621 / 7623

页数：3

共 25 条

[21] Ruthenium-catalyzed [2+2] cycloadditions between bicyclic alkenes and alkynyl halides [J].