DFT Mechanistic Account for the Site Selectivity of Electron-Rich C(sp3)-H Bond in the Manganese-Catalyzed Aminations.,Organic Letters

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DFT Mechanistic Account for the Site Selectivity of Electron-Rich C(sp3)-H Bond in the Manganese-Catalyzed Aminations.
Organic Letters ( IF 4.9 ) Pub Date : 2020-01-08 , DOI: 10.1021/acs.orglett.9b04215
Zheyuan Liu ₁ , Yu Lu ₂ , Jiandong Guo ₂ , Wenping Hu ₁ , Yanfeng Dang ₁ , Zhi-Xiang Wang ₂

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DFT study suggests that the C-H cleavage involved in the C(sp3)-H amination catalyzed by manganese perchlorophthalocyanine complex [MnIII(ClPc)]+ proceeds via hydride transfer (HYT), instead of hydrogen atom transfer (HAT), thus elucidating why the reaction favors aminating the electron-rich C-H bond, rather than that with smaller bond dissociation energy preferred by HAT. Detailed analyses indicate the HYT actually occurs via concerted electron and hydrogen atom transfers and the redox-active ClPc ligand enables the HYT.

中文翻译：

DFT机制说明了锰催化胺中富电子的C（sp3）-H键的位选择性。

DFT研究表明，锰全氯酞菁配合物[MnIII（ClPc）] +催化的C（sp3）-H胺化反应中的CH裂解是通过氢化物转移（HYT）而不是氢原子转移（HAT）进行的，因此阐明了为什么反应有利于胺化富电子的CH键，而不是具有较小的HAT首选的键离解能。详细的分析表明，HYT实际上是通过协调的电子和氢原子转移发生的，并且具有氧化还原活性的ClPc配体可以实现HYT。

更新日期：2020-01-08

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