Diazo ketones derived from Np-tolylsulfonyl (tosyl)-protected α-and β-amino acids have been synthesized and their diazo decomposition under standard Wolff rearrangement conditions, PhCO2Ag–Et3N–MeOH, has been investigated. It is observed that, under these conditions, several different reaction pathways, including direct carbene N–H insertion, are possible. The reaction is markedly affected by the N-protecting group, the substrate ...