Gold-Catalyzed Reactions via Cyclopropyl Gold Carbene-like Intermediates.
Gold-Catalyzed Reactions via Cyclopropyl Gold Carbene-like Intermediates.
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DOI：
10.1021/acs.joc.5b01106
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发表时间：
2015-08-07
期刊：
影响因子：
--
通讯作者：
Echavarren AM
中科院分区：
文献类型：
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作者：
Dorel R;Echavarren AM
金（I）催化的1，n-烯炔环异构化反应是通过具有高度扭曲的环丙基金（I）卡宾结构的亲电物种进行的，该亲电物种可以与不同的亲核试剂反应，通过攻击环丙烷或卡宾碳形成各种各样的产物。特别重要的是其中金（I）卡宾与烯烃反应以分子内或分子间形成环丙烷的反应。在不存在亲核试剂的情况下，1，n-烯炔导致多种环异构化产物，包括由骨架重排产生的那些。通过环丙基金（I）卡宾类中间体进行的反应理想地适合于通过选择性活化高度官能化的烯炔或多烯炔中的炔来生物启发合成萜类天然产物。
Cycloisomerizations of 1,n-enynes catalyzed by gold(I) proceed via electrophilic species with a highly distorted cyclopropyl gold(I) carbene-like structure, which can react with different nucleophiles to form a wide variety of products by attack at the cyclopropane or the carbene carbons. Particularly important are reactions in which the gold(I) carbene reacts with alkenes to form cyclopropanes either intra- or intermolecularly. In the absence of nucleophiles, 1,n-enynes lead to a variety of cycloisomerized products including those resulting from skeletal rearrangements. Reactions proceeding through cyclopropyl gold(I) carbene-like intermediates are ideally suited for the bioinspired synthesis of terpenoid natural products by the selective activation of the alkyne in highly functionalized enynes or polyenynes.