Carbon-carbon bond cleavage reactions of 1,2-diamines initiated by photoinduced electron transfer

Abstract

The oxidative photofragmentations of a series of 1,2-diamines have been studied in reaction with photoexcited electron acceptors under a variety of conditions. All the diamines were found to undergo a clean two electron redox reaction (in the presence of trace amounts of water) to produce after cleavage, two free amines, two aldehydes, and the reduced acceptor. Investigation of the role of variables (solvent, acceptor, temperature, isotope effects, etc.) on the quantum yields for diamine fragmentation leads to a mechanistic picture in which the critical step in the reaction is an unassisted fragmentation. Although formally similar to the photoreactions of previously studied aminoalcohols, the photoinduced electron transfer fragmentation reaction of 1,2-diamines shows key mechanistic differences and is apparently both a more general reaction and significantly more rapid in several cases.