In despite of its wide utility in organic synthesis and bio-research field, synthetic approach to thioester has been majorly relied on classical coupling reactions. Nature utilizes different pathway for thioester synthesis. For example, methylmalonyl-CoA mutase (MCM) catalyzes succinyl-CoA synthesis by direct transfer of thioester group into sp3 hybridized carbon with C-H activation strategy. Inspired by that, we developed the first transition metal catalyzed selective C(sp3)-H thioesterification reaction. From stable and easily synthesizable aryl thiobenzoate, thioester group is selectively transferred to α-oxo carbon of ether by mild C-H activation. Notably, the reaction is driven by visible light, so it can be performed at room temperature without any stoichiometric amount of oxidant or reductant. We believe that it can be not only an ideal alternative of classical thioester synthetic strategy, but also a promising preliminary strategy for synthesis of synthetically important α-oxo carboxylic acid derivatives.

Selective α-oxo C(sp3)-H thioesterification of ether

253rd National Meeting (2017)

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