New Rhodium-Catalyzed Allylic Alkylation Reactions

描述（由申请人提供）：以下提案的目的是开发区域特异性和对映体特异性铑催化的烯丙基取代作为一般交叉偶联反应，以及与自由基环化和新型金属催化的碳环化反应的组合。预计这些过程将有助于设计和应用新的策略，使生物学重要分子的快速全合成。 具体关注领域概述如下： 新的烯丙基胺化反应与环状乙烯基酰胺和脲：新的烯丙基胺化反应与乙烯基酰胺和脲的发展，用于生物碱，lepadiformine和batzelladine D的全合成。 新的金属催化的碳环化反应：使用手性铑络合物的对映选择性金属催化的[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。一种暂时的硅栓（TST）铑催化的[4+2+2]碳环化方法的二萜，环氧dictymene的发展。

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.