Department of Chemistry and Biochemistry, The University of Texas at Dallas, 800 West Campbell Road, Richardson, Texas 75080-3021, United States.
J Am Chem Soc. 2020 Jun 3;142(22):9932-9937. doi: 10.1021/jacs.0c03993. Epub 2020 May 19.
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 π-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.
发展了一种光诱导钯催化的共轭二烯 1,2-碳官能化反应。这种温和的模块化方法不需要使用外源光敏剂和外部氧化剂，能够从易得的 1,3-二烯、碘代烷和胺高效、高区域和立体选择性地合成广泛的烯丙基胺。还证明了 O-和 C-亲核试剂对氧烷基化和二烷基化产物的应用。提出了一个假定的π-烯丙基钯自由基-极性交叉途径作为这个三组分偶联过程中的关键事件。该协议的实用性通过其在几种含胺药物的衍生化中的应用得到了强调。
