[Ru(IV)(por)Cl(2)] (por = porphyrin dianion) can efficiently catalyze nitrene insertion into aldehyde C-H bonds with phosphoryl azides as a nitrene source to give N-acylphosphoramidates in good to high yields.

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[Ru(IV)(F20-TPP)Cl2][H2(F20-TPP) = meso-tetrakis(pentafluorophenyl)porphyrin] is an active catalyst for both inter- and intra-molecular nitrene insertion into sp(3) C-H bonds of hydrocarbons in good to high product yields using phosphoryl azides as nitrene sources.