Photoinduced Palladium-Catalyzed Carbofunctionalization of Conjugated Dienes Proceeding via Radical-Polar Crossover Scenario: 1,2-Aminoalkylation and Beyond
Photoinduced Palladium-Catalyzed Carbofunctionalization of Conjugated Dienes Proceeding via Radical-Polar Crossover Scenario: 1,2-Aminoalkylation and Beyond
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DOI：
10.1021/jacs.0c03993
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发表时间：
2020-06-03
影响因子：
15
通讯作者：
Gevorgyan, Vladimir
中科院分区：
文献类型：
--
作者：
Cheung, Kelvin Pak Shing;Kurandina, Daria;Gevorgyan, Vladimir
发展了一种光诱导钯催化共轭二烯的1，2-碳官能化反应。这种温和的模块化方法，它不需要使用外源光敏剂和外部氧化剂，允许从容易获得的1，3-二烯，烷基碘和胺的有效和高度区域和立体选择性的合成范围广泛的烯丙基胺。还证明了O-和C-亲核试剂对烷氧基化和二烷基化产物的使用。一个假定的π-烯丙基钯自由基极性交叉路径被提出作为一个关键事件，在这个三组分耦合过程。该协议的效用是突出了其应用程序的衍生化的几个含胺的药物。
A photoinduced palladium-catalyzed 1,2-carbofunctionalization of conjugated dienes has been developed. This mild modular approach, which does not require employment of exogeneous photosensitizers and external oxidants, allows for efficient and highly regio- and stereoselective synthesis of a broad range of allylic amines from readily available 1,3-dienes, alkyl iodides, and amines. Employment of O- and C-nucleophiles toward oxyalkylation and dialkylation products was also demonstrated. A putative pi-allyl palladium radical-polar crossover path is proposed as a key event in this three-component coupling process. The utility of this protocol is highlighted by its application for derivatization of several amine-containing drugs.