β-Lactam-Forming Photochemical Reactions of N-Trimethylsilylmethyl-and N-Tributylstannylmethyl-Substituted α-Ketoamides

摘要

Two mechanisms have been proposed for the β-lactam-forming photochemical reactions of α-ketoamides. One, suggested by Aoyama, involves excited-state H-atom abstraction while the other, put forth by Whitten, follows a sequential SET-proton-transfer route. The photochemical properties of N-trimethylsilylmethyl-and N-tributylstannylmethyl-substituted α-ketoamides were explored in order to gain information about the mechanism of this process and to develop a regioselective method for β-lactam formation. The results of this effort show that photoreactions of N-trimethyl-silylmethyl-substituted α-ketoamides proceed by competitive H-atom abstraction and sequential SET-desilylation pathways and a sequential SET-destannylation pathway is preferentially followed in photochemical reactions of the tributylstannylmethyl-substituted α-ketoamides.