Regio- and enantioselective intermolecular rhodium-catalyzed [2+2+2] carbocyclization reactions of 1,6-enynes with methyl arylpropiolates
Regio- and enantioselective intermolecular rhodium-catalyzed [2+2+2] carbocyclization reactions of 1,6-enynes with methyl arylpropiolates
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DOI：
10.1021/ja053123y
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发表时间：
2005-09-14
影响因子：
15
通讯作者：
Sawyer, JR
中科院分区：
文献类型：
--
作者：
Evans, PA;Lai, KW;Sawyer, JR
过渡金属催化的[m+n+o]碳环化反应为构建复杂的多环体系提供了强有力的方法，这些体系通常不能通过经典的周环反应获得。我们首次发展了铑催化的含碳和杂原子的1，6-烯炔与不对称1，2-二取代炔的[2+2+2]碳环化反应。这项研究清楚地描绘了获得优异的区域和对映体选择性的配体要求。此外，利用各种吸电子基团和引入季碳立体中心的能力提供了其应用于靶向合成所需的多功能性水平。目前正在对这种新方法在天然产物全合成中的开发和应用进行进一步的研究。
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 crossedintermolecular 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.