Regio- and Enantioselective Intermolecular Rhodium-Catalyzed [2+2+2] Carbocyclization Reactions of 1,6-Enynes with Methyl Arylpropiolates

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• 作者：P. Andrew Evans ; Kwong Wah Lai ; and James R. Sawyer
• 刊名：Journal of the American Chemical Society
• 出版年：2005
• 出版时间：September 14, 2005
• 年：2005
• 卷：127
• 期：36
• 页码：12466 - 12467
• 全文大小：46K
• 年卷期：v.127,no.36(September 14, 2005)
• ISSN：1520-5126

文摘

Transition metal-catalyzed [m+n+o] carbocyclization reactions provide powerful methods for the construction of complex polycyclic systems that are generally not accessible through classical pericyclic reactions. We have developed the first regio- and enantioselective crossed intermolecular rhodium-catalyzed [2+2+2] carbocyclization of carbon- and heteroatom-tethered 1,6-enynes with unsymmetrical 1,2-disubstituted alkynes. This study clearly delineates the ligand requirements for obtaining excellent regio- and enantioselectivity. Furthermore, the ability to utilize various electron-withdrawing groups, and to introduce quaternary carbon stereogenic centers, provides the level of versatility necessary for its application to target-directed synthesis. Additional studies on the development and application of this novel methodology to the total synthesis of natural products are currently underway.