Citation: Yang Yinuo, Zhang Qi, Shi Jing, Fu Yao. Mechanism Study of Mn(I) Complex-catalyzed Imines and Alkynes Dehydrogenation Coupling Reaction[J]. Acta Chimica Sinica, ;2016, 74(5): 422-428. doi: 10.6023/A15110736 shu

Mechanism Study of Mn(I) Complex-catalyzed Imines and Alkynes Dehydrogenation Coupling Reaction

Yang Yinuo ,
Zhang Qi ,
Shi Jing ^*,, ,
Fu Yao ^*,,

1.
Department of Chemistry, University of Science and Technology of China, Hefei 230026

Corresponding author: Shi Jing, shijing@ustc.edu.cn Fu Yao, fuyao@ustc.edu.cn
Received Date: 21 November 2015

Fund Project: Fundamental Research Funds for the Central Universities WK2060190025the National Natural Science Foundation of China 21325208Fundamental Research Funds for the Central Universities FRF-TP-14-015A2the National Natural Science Foundation of China 21361140372the National Natural Science Foundation of China 21202006973 Program 2012CB215306Science Foundation of The Chinese Academy of Sciences KJCX2-EW-J02the National Natural Science Foundation of China 21172209Fundamental Research Funds for the Central Universities WK2060190040

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With the development and widespread use of transition metal catalysts, C—H activation has become a hot topic in organic synthesis, especially in the construction of C—C bond of organic compounds. As an important and cheap catalyst, manganese complex has shown great potential for catalyzing C—H activation both in academic and industrial applications. In this paper, the mechanism of manganese-catalyzed dehydrogenative [4+2] annulation by C—H/N—H activation was investigated systematically with the aid of density functional theory (DFT) calculations in 1, 4-dioxane solvent. In detail, we use M06-L/[SDD:6-311+G(d, p)(SMD)]//M06-L/[LANL2DZ:6-31G(d)] to examine the Gibbs free energy, structure and other properties of possible intermediates and transition states in this catalytic cycle. By comprehensive comparison and discussion, we obtained a favorable pathway consisting of five steps: (1) catalyst initiation occurred with the assistance of bromine anion rather than imide to form active catalyst; (2) alkyne inserted into the active catalyst to generate a seven-membered manganacycle after dissociation of a carbon monoxide; (3) double bond migration happened in this seven-membered manganacycle to form a product precursor; (4) the product precursor would dissociate by β-H elimination and generated product isoquinoline and active Mn—H complex; (5) the active Mn—H complex was subsequently combined with an imine followed by dehydrogenative C—H activation to complete the whole catalytic cycle. In this context, the reason for the highly atom-economical C—H activation by direct dehydrogenation (eliminates the necessity for oxidants or additives) has been clarified by this mechanism. The present study was aimed at further understanding of Mn(I)-catalyzed dehydrogenative C—H activation, and provided more theoretical basis for future more Mn-catalyzed C—H activation.
- manganese-catalyzed,
- density functional theory (DFT),
- C—H activation,
- mechanism
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