The synthesis of amide C�N bonds via nucleophilic acyl substitutions constitutes one of the most fundamental transformations in chemical synthesis. Many of the current amidation methods utilize harsh reaction conditions and produce undesired byproducts. Through implementation of chlorophosphites and azides, we have established a highly chemoselective, direct nucleophilic acyl substitution of carboxylic acids which affords excellent yields of analytically pure amides after a simple aqueous workup. This method has also been applied to the synthesis of an assortment of natural and unnatural dipeptides with retention of stereochemistry.In addition, we have focused our efforts towards the minimization of molecular waste through the development of a catalytic variant using a mild silane reductant. We are currently applying these phosphite and phosphine-mediated rearrangement processes in various systems to advance C�N bond forming methods and these results will be presented.

Application of phosphorus-mediated rearrangements towards C-N bond formation

246th National Meeting (2013)

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