Photocatalysis offers an efficient, energy-saving and environmentally-friendly pathway for benzaldoxime synthesis. Inspired by the secondary coordination sphere of nitrite reductase, we report herein the first photocatalytic benzaldoxime synthesis from NO2- and benzyl alcohol. Different from introducing co-catalysts, the integration of glutathione (GSH) relay with CdS quantum dots (QDs) can effectively mediate hole transfer and facilitate selective benzyl alcohol oxidation to benzaldehyde. At the same time, GSH assists continuous proton transfer to promote selective 4e-/5H+ NO2- reduction and form NH2OH in-situ. As a result, the synergic C-N coupling delivers a series of benzyl oximes from NO2- and benzyl alcohols with excellent yield and selectivity. Benzaldoxime synthesis proceeds at a rate of 18.7 mmol gcat-1 h-1 and TON of 52,875, accomplishing 90.6 % benzyl alcohol conversion and 72.3 % benzaldoxime yield, which is comparable to the best records for electrocatalytic benzaldoxime synthesis. The scaled reaction to produce 0.58 g benzaldoxime with a yield of 41 % demonstrates efficient, atom-economic and step-economic photocatalytic oxime synthesis via selective C-N coupling from abundant resources.
Keywords: C-N coupling; CdS quantum dot; Glutathione; Photocatalysis; benzaldoxime.
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