Theoretical studies on Mn-catalyzed intermolecular allylic C-H aminations of internal olefins: mechanism, chemo- and regioselectivity

摘要

The mechanism, chemo-and regioselectivity of Mn-catalyzed intermolecular C-H amination of internal olefin have been studied using B3LYP functional. The internal allylic C-H amination mechanism involves three steps: PhI extrusion, Hydride transfer and in situ coupling of C and N atoms. More importantly, the origin of regioselectivity is revealed via comparative investigations into aminations of three alkene substrates. Based on our calculated results, one can expect that for a new Mn-catalyzed internal olefin amination system, the regioselectivity toward in situ generation of amine can be significantly increased via the introduction of a bulky, strong electron-withdrawing group on the substrate at the position away from the targeted C-H bond. Such a Mncatalyzed regioselectivity was theoretically investigated for the first time, which is useful toward the future design and development of highly regioselective amination system.

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