The photochemistry of mixed anhydrides: A search for selectivity in photochemically initiated bond cleavage reactions

Article abstract of DOI:10.1021/ja00054a012

A number of mixed anhydrides (RC(O)OC(O)R') have been synthesized for the purpose of exploring the regioselectivity of their photochemical reactions. The photochemical reaction products, quantum yields, and reaction rates have been determined. For those compounds containing no α-hydrogens, high regioselectivity is obtained upon irradiation and can be understood on the basis of the relative C-O bond dissociation energies. The reaction can be quenched by intramolecular electron transfer. For those compounds containing α-hydrogen atoms, the Norrish type II reaction is faster than the corresponding C-O cleavage reactions, resulting in poor regioselectivity.