Catalytic Amino Group Transfer Reactions Mediated by Photoinduced Nitrene Formation from Rhodium-Hydroxamates
Hoimin Jung1, Jeonguk Kweon1, Jong-Min Suh2
1Center for Catalytic Hydrocarbon Functionalizations, Institute for Basic Science (IBS), Daejeon 34141, South Korea & Department of Chemistry, Korea Advanced Institute of Science and Technology (KAIST), Daejeon, 34141, South Korea.
Abstract:
Herein, we report a photocatalytic platform to access transient nitrenoids by designing photo-responsive neutral rhodium-hydroxamate complexes. Combined experimental and computational mechanistic studies, including electron paramagnetic resonance (EPR) and mass spectrometric analysis, suggest that electrophilic Fischer-type Rh-acylnitrenoid intermediates could be generated via photoactivation of corresponding Rh-hydroxamates via N-O bond homolysis and redox event. Moreover, catalytic acylnitrenoid transfer was explored toward the amidation of various hydrocarbons, amines, and alcohols to furnish new N-C, N-N, and N-O bonds.
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