Photocatalytic Cleavage of C(sp3)−N Bond in Trialkylamines to Dialkylamines and Olefins

Development of a new and green strategy for C(sp3)−N bond cleavage is very interesting. Herein, photocatalytic cleavage of the C(sp3)−N bond of trialkylamines was achieved, with concurrent formation of dialkylamines and olefins. It was found that a rationally designed 2D‐Bi2WO6@1D‐LaPO4 heterostructure was very efficient for the reaction due to its high light collection efficiency and unique catalytic properties. The strategy could be used for different trialkylamines, including triethylamine, tri‐n‐propylamine, and ethyl‐di‐isopropylamine. The mechanistic investigation indicated that the catalyst with heterostructure was not only favorable for charge carrier separation but also rendered excited electrons with high reduction capacity. This work opens a way for C(sp3)−N bond cleavage of trialkylamines. C−N cleavage: A rationally designed heterojunction of 2D‐Bi2WO6@1D‐LaPO4 is innovatively assembled for photocatalytic C(sp3)−N bond cleavage under ambient conditions, presenting a new and green strategy for dialkylamine synthesis from trialkylamines, with concurrent formation of the corresponding olefins.