Kvasovs Nikita, Fang Jian, Kliuev Fedor, Gevorgyan Vladimir
Department of Chemistry and Biochemistry, The University of Texas at Dallas, Richardson, Texas 75080-3021, United States.
J Am Chem Soc. 2023 Aug 23;145(33):18497-18505. doi: 10.1021/jacs.3c04968. Epub 2023 Aug 9.
A visible light-induced palladium-catalyzed homologative three-component synthesis of allylic amines has been developed. This protocol proceeds a unique mechanism involving two distinct cycles enabled by the same Pd(0) catalyst: a visible light-induced hybrid radical alkyl Heck reaction between 1,1-dielectrophile and styrene, followed by the "in dark" classical Tsuji-Trost-type allylic substitution reaction. This method works well with a broad range of primary and secondary amines, aryl alkenes, dielectrophiles, and in complex settings. The regiochemistry of the obtained products is primarily governed by the structure of 1,1-dielectrophile. Involvement of π-allyl palladium intermediates allowed for the control of stereoselectivity, which has been demonstrated with up to 95:5 er.
已开发出一种可见光诱导的钯催化烯丙基胺的同系化三组分合成方法。该反应历程遵循一种独特的机理，涉及由同一Pd(0)催化剂实现的两个不同循环：1,1 - 双亲电试剂与苯乙烯之间的可见光诱导混合自由基烷基Heck反应，随后是“黑暗中”的经典Tsuji - Trost型烯丙基取代反应。该方法适用于多种伯胺和仲胺、芳基烯烃、双亲电试剂，且适用于复杂体系。所得产物的区域化学主要由1,1 - 双亲电试剂的结构决定。π - 烯丙基钯中间体的参与使得立体选择性得以控制，高达95:5的对映体过量已得到证实。
