Comprehensive Mechanistic Insight into Cooperative Lewis Acid/Cp*CoIII-Catalyzed C-H/N-H Activation for the Synthesis of Isoquinolin-3-ones

Qiong Wang; Fang Huang; Langhuan Jiang; Chuanxue Zhang; Chuanzhi Sun; Jianbiao Liu; Dezhan Chen

doi:10.1021/acs.inorgchem.7b03216

Comprehensive Mechanistic Insight into Cooperative Lewis Acid/Cp*Co^III-Catalyzed C-H/N-H Activation for the Synthesis of Isoquinolin-3-ones

Inorg Chem. 2018 Mar 5;57(5):2804-2814. doi: 10.1021/acs.inorgchem.7b03216. Epub 2018 Feb 15.

Authors

Qiong Wang¹, Fang Huang¹, Langhuan Jiang¹, Chuanxue Zhang¹, Chuanzhi Sun¹, Jianbiao Liu¹, Dezhan Chen¹

Affiliation

¹ College of Chemistry, Chemical Engineering and Materials Science, Collaborative Innovation Center of Functionalized Probes for Chemical Imaging in Universities of Shandong, Key Laboratory of Molecular and Nano Probes, Ministry of Education, Shandong Provincial Key Laboratory of Clean Production of Fine Chemicals , Shandong Normal University , Jinan 250014 , P. R. China.

PMID: 29446928
DOI: 10.1021/acs.inorgchem.7b03216

Abstract

The mechanism of B(C₆F₅)₃ promoted Cp*Co^III-catalyzed C-H functionalization was investigated in detail employing density functional theory (DFT). The formation free energy of every possible species in the multicomponent complex system was explored and the optimal active catalyst was screened out. The results uncover the role of B(C₆F₅)₃ played in forming active catalyst is from the coordination with OAc^-, but not from the formation of [I(C₆F₅)₃B]^-, and no acceleration effect is found in C-H activation as well as the formation of Co^III-carbene intermediate. Moreover, present theoretical results elucidate the Cp*Co^III-catalyzed C-H activation is mediated by imine N-coordination other than general proposed the sequence of N-deprotonation directed C-H activation. The metal-controlled C-H/N-H selectivity was then elucidated by insighting into [Cp*Co^IIIOAc]⁺/[Cp*Rh^IIIOAc]⁺-catalyzed C-H and N-H activations, respectively.