Computationally Designed and Experimentally Confirmed Diastereoselective Rhodium-Catalyzed Pauson鈭扠hand Reaction at Room Temperature
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- 作者：Mu-Hyun Baik ; Shivnath Mazumder ; Paolo Ricci ; James R. Sawyer ; Ye-Geun Song ; Huijun Wang ; P. Andrew Evans
- 刊名：Journal of the American Chemical Society
- 出版年：2011
- 出版时间：May 25, 2011
- 年：2011
- 卷：133
- 期：20
- 页码：7621-7623
- 全文大小：695K
- 年卷期：v.133,no.20(May 25, 2011)
- ISSN：1520-5126
文摘
The computational analysis of the rhodium-catalyzed Pauson鈭扠hand 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 蟽-electron-withdrawing group to promote polarization and thereby reduce the activation barrier to provide a highly diastereoselective reaction at room temperature.