TY - JOUR T1 - Catalyst-Controlled and Tunable, Chemoselective Silver-Catalyzed Intermolecular Nitrene Transfer: Experimental and Computational Studies JF - Journal of the American Chemical Society Y1 - 2016 A1 - Dolan, Nicholas A1 - Scamp, Ryan J. A1 - Yang, Tzuhsiung A1 - Berry, John F. A1 - Schomaker, Jennifer M. AB -

The development of new catalysts for selective nitrene transfer is a continuing area of interest. In particular, the ability to control the chemoselectivity of intermolecular nitrene transfer in the presence of multiple reactive sites has been a long-standing challenge in the field. In this paper, we demonstrate the first examples of silver-catalyzed, non-directed, intermolecular nitrene transfer reactions that are both chemoselective and flexible for aziridination or C–H insertion, depending on the choice of ligand. Experimental probes present a puzzling picture of the mechanistic details of the pathways mediated by [(tBu3tpy)AgOTf]2 and (tpa)AgOTf. Computational studies elucidate these subtleties and provide guidance for the future development of new catalysts exhibiting tunability in group transfer reactions.

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