Merging of Light/Dark Palladium Catalytic Cycles Enables Multicomponent Tandem Alkyl Heck/Tsuji-Trost Homologative Amination Reaction toward Allylic Amines.
Merging of Light/Dark Palladium Catalytic Cycles Enables Multicomponent Tandem Alkyl Heck/Tsuji-Trost Homologative Amination Reaction toward Allylic Amines.
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DOI：
10.1021/jacs.3c04968
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发表时间：
2023-08
影响因子：
15
通讯作者：
Nikita Kvasovs;Jian Fang;Fedor Kliuev;V. Gevorgyan
中科院分区：
文献类型：
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作者：
Nikita Kvasovs;Jian Fang;Fedor Kliuev;V. Gevorgyan
研究了一种可见光诱导钯催化的烯丙胺同源三组分合成方法。该方案通过一种独特的机制进行，涉及由相同的Pd(0)催化剂激活的两个不同的循环：在可见光诱导的1,1-亲电试剂和苯乙烯之间的杂化自由基烷基Heck反应，然后是“黑暗”的经典tsuji - trost型烯丙基取代反应。该方法适用于广泛的伯胺和仲胺，芳基烯烃，亲电试剂和复杂的设置。所得产物的区域化学主要由1,1-亲电试剂的结构决定。π-烯丙基钯中间体的参与允许控制立体选择性，这已被证明高达95:5的er。
A visible light-induced palladium-catalyzed homologative three-component synthesis of allylic amines has been developed. This protocol proceeds via 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.