New Rhodium-Catalyzed Allylic Alkylation Reactions

描述(由申请人提供)：以下建议的目的是开发区域和对映异构体催化的烯丙基取代反应，作为一种一般的交叉偶联反应，并与自由基环化和新型金属催化的碳环化反应相结合。预计这些过程将促进新策略的设计和应用，从而实现生物重要分子的快速全合成。 具体感兴趣的领域摘要如下： 与环烯丙基酰胺和尿素的新的烯丙基胺化反应：与乙烯基酰胺和尿素的新的烯丙胺化反应，用于生物碱、来帕双胺和巴采拉定D的全合成。 新的金属催化的碳环化反应：使用手性铑配合物的不对称金属催化的[2 2 2]碳环化反应，以及与烯丙基取代的组合用于新的串联过程。发展了一种临时的硅系留(TST)Rh催化的[4 2 2]碳环化方法来合成二萜环氧丁二烯。

DESCRIPTION (provided by applicant): The aim of the following proposal is the development of the regio- and enantiospecific rhodium-catalyzed allylic substitution as a general cross-coupling reaction, and the combination with free radical cyclization and novel metal-catalyzed carbocyclization reactions. It is anticipated that these processes will facilitate the design and application of novel strategies that permit the expeditious total synthesis of the biological important molecules. The specific areas of interest are summarized as follows: New Allylic Amination Reactions with Cyclic Vinylogous Amides and Ureas: the development of new allylic amination reactions with vinylogous amides and ureas for the total synthesis of the alkaloids, lepadiformine and batzelladine D. New Metal-Catalyzed Carbocyclization Reactions: enantioselective metal-catalyzed [2+2+2] carbocyclization reactions using chiral rhodium complexes, and the combination with allylic substitutions for new tandem processes. The development of a temporary silicon-tethered (TST) rhodium-catalyzed [4+2+2] carbocyclization approach to the diterpene, epoxydictymene.