(Methyl)tetratolylporphyrinatoiridium (Ir(TTP)CH3) catalyzed the N�H insertion reactions between ethyl diazoacetate (EDA) or methyl phenyldiazoacetate (MPDA) and a variety of aryl, aliphatic, primary, and secondary amines. These reactions proceeded with yields generally greater than 70% and with up to 105 catalyst turnovers. Reactions between primary amines and EDA could be optimized to generate either single- or double-insertion products selectively. Furthermore, mixed trisubstituted glycine esters could be produced from the insertion of one equivalent of EDA and one equivalent of MPDA into primary amines. The reaction mechanism was explored by kinetics investigations, linear free energy relationships, trapping experiments, and isotope-labeling studies. Reversible amine binding to the catalyst had a significant inhibitory effect on reaction rate; equilibrium constants for the binding between Ir(TTP)CH3 and several N-alkyl and para-substituted anilines were in the range of 102�105. A metalloporphyrin intermediate consistent with a metal-ylide complex was observed by absorption spectroscopy.

N-H insertion reactions catalyzed by (methyl)tetratolylporphyrinatoiridium

246th National Meeting (2013)

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