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An efficient metal-free aerobic oxidative C–N bond cleavage of tertiary amines has been developed to construct N-heterocycles using molecular oxygen as the sole oxidant with high atom efficiency, in which all of the three alkyl groups in tertiary amines can be utilized and transformed into N-heterocycles.

Graphical abstract: Metal-free aerobic oxidative C–N bond cleavage of tertiary amines for the synthesis of N-heterocycles with high atom efficiency

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