Regio- and enantioselective intermolecular rhodium-catalyzed [2+2+2] carbocyclization reactions of 1,6-enynes with methyl arylpropiolates

被引:103
作者
Evans, PA [1 ]
Lai, KW [1 ]
Sawyer, JR [1 ]
机构
[1] Indiana Univ, Dept Chem, Bloomington, IN 47405 USA
关键词
D O I
10.1021/ja053123y
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
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. Copyright © 2005 American Chemical Society.
引用
收藏
页码:12466 / 12467
页数:2
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