A Counterion/Ligand-Tuned Chemo- and Enantioselective Copper-Catalyzed Intermolecular Radical 1,2-Carboamination of Alkenes
作者:Xian-Yan Cheng、Yu-Feng Zhang、Jia-Huan Wang、Qiang-Shuai Gu、Zhong-Liang Li、Xin-Yuan Liu
DOI:10.1021/jacs.2c08035
日期:2022.10.5
design of a counterion/highly sterically demanded ligand coeffect to promote the ligand exchange of copper(I) with sulfoximines and forge chiral C–N bonds between alkyl radicals and the chiral copper(II) complex. The reaction covers alkenes bearing distinct electronic properties, such as aryl-, heteroaryl-, carbonyl-, and aminocarbonyl-substituted ones, and various radical precursors, including alkyl
铜催化的烯烃对映选择性自由基 1,2-carboamination 与易于获得的烷基卤化物是生产手性胺支架的一种有吸引力的策略。挑战来自烷基卤化物和烯烃之间容易发生的原子转移自由基加成以及对映控制问题。我们在此描述了一种自由基烯烃 1,2-carboamination 与亚砜亚胺以高度化学和对映选择性的方式。该过程成功的关键是反离子/高度空间要求的配体协同效应的概念设计,以促进铜(I)与亚砜亚胺的配体交换,并在烷基自由基和手性铜(II)之间形成手性 C-N 键复杂的。该反应涵盖了具有不同电子特性的烯烃,例如芳基-、杂芳基-、羰基-、3来源。简便的转化提供了许多有机合成和相关领域感兴趣的手性胺构建块。