Photoredox/Iron Dual-Catalyzed Insertion of Acyl Nitrenes into C–H Bonds

In
this work, the use of N-acyloxybenzamides as
efficient acyl nitrene precursors under photoredox/iron dual catalysis
is reported. The resulting acyl nitrenes could be captured by various
types of C–H bonds and S- or P-containing molecules. Mechanism
investigations suggested that the formation of the acyl nitrene from
the N-acyloxybenzamide occurs by a photoredox process,
and it is believed that in this redox process oxidative N–H
bond cleavage of the N-acyloxybenzamide occurs prior
to reductive N–O bond cleavage of the N-acyloxybenzamide.

本研究报道了N-酰氧基苯甲酰胺（N-acyloxybenzamides）作为高效酰基氮宾（acyl nitrene）前体，在光氧化还原/铁双催化体系下的应用。所生成的酰基氮宾可被各类碳氢键以及含硫、含磷分子捕获。机理研究表明，N-酰氧基苯甲酰胺经由光氧化还原过程生成酰基氮宾，且该氧化还原过程中，N-酰氧基苯甲酰胺的氧化性N-H键断裂先于其还原性N-O键断裂发生。