Catalyst-free photodecarbonylation of ortho-amino benzaldehyde?

Green Chemistry Pub Date: 2020-05-07 DOI: 10.1039/D0GC01256D

Abstract

It is almost a consensus that decarbonylation of the aldehyde group (–CHO) needs to not only be mediated by transition metal catalysts, but also requires severe reaction conditions (high temperature and long reaction time). In this work, inspired by the “conformational-selectivity-based” design strategy, we broke this consensus and discovered a catalyst-free photodecarbonylation of the aldehyde group. It revealed that decarbonylation can be easily achieved with visible light irradiation by introducing a tertiary amine into the ortho-position of the aldehyde group. A diverse array of tertiary amines is tolerated by our photodecarbonylation under mild conditions. Furthermore, the (QM) computations of the mechanism and the experiments on well-designed special substrates revealed that our photodecarbonylation depends on the conformational specificity of the aldehyde group and tertiary amine, and occurs through an unusual [1,4]-H shift and a subsequent [1,3]-H shift.

Graphical abstract: Catalyst-free photodecarbonylation of ortho-amino benzaldehyde
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