Nondirected, Cu-Catalyzed sp3 C-H Aminations with Hydroxylamine-Based Amination Reagents: Catalytic and Mechanistic Studies.
Nondirected, Cu-Catalyzed sp3 C-H Aminations with Hydroxylamine-Based Amination Reagents: Catalytic and Mechanistic Studies.
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DOI：
10.1021/acs.organomet.7b00003
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发表时间：
2017-03
期刊：
影响因子：
2.8
通讯作者：
Anqi Wang;N. Venditto;Julia W. Darcy;M. Emmert
中科院分区：
文献类型：
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作者：
Anqi Wang;N. Venditto;Julia W. Darcy;M. Emmert
本工作证明了使用羟胺基胺化试剂RSO 2 NH-0Ac用于苄基C-H键的非定向、Cu催化的胺化。胺化试剂可以以克规模制备，是工作台稳定的，并且以高达86%的产率提供苄基C-H胺化产物。与甲苯作为底物建立的反应性的机理研究揭示了配体促进，铜催化的机制进行通过Ph-CH 2（NTsOAc）作为主要中间体。Ph-CH 2（NTsOAc）生成Ph-CH 2-NHTs的化学计量反应性表明C-H胺化的两循环自由基途径，其中所用二亚胺配体的分解起重要作用。
This work demonstrates the use of hydroxylamine-based amination reagents RSO2NH-OAc for the nondirected, Cu-catalyzed amination of benzylic C-H bonds. The amination reagents can be prepared on a gram scale, are benchtop stable, and provide benzylic C-H amination products with up to 86% yield. Mechanistic studies of the established reactivity with toluene as substrate reveal a ligand-promoted, Cu-catalyzed mechanism proceeding through Ph-CH2(NTsOAc) as a major intermediate. Stoichiometric reactivity of Ph-CH2(NTsOAc) to produce Ph-CH2-NHTs suggests a two-cycle, radical pathway for C-H amination, in which the decomposition of the employed diimine ligands plays an important role.