Richard S. Givens, Kenneth Stensrud, Peter G. Conrad, II., Abraham L. Yousef, Chamani Perera, Sanjeewa N. Senadheera, Dominik Heger, Jakob Wirz, "p-Hydroxyphenacyl Photoremovable Protecting Groups: Robust Photochemistry Despite Substituent Diversity", Can. J. Chem. 2011, 89, 364-384.


Abstract: A broadly based investigation of the effects of a diverse array of substituents on the photochemical rearrangement of p-hydroxyphenacyl esters has demonstrated that common substituents such as F, MeO, CN, CO2R, CONH2, and CH3 have little effect on the rate and quantum efficiencies for the photo-Favorskii rearrangement and the release of the acid leaving group or on the lifetimes of the reactive triplet state. A decrease in the quantum yields across all substitutents was observed for the release and rearrangement when the photolyses were carried out in buffered aqueous media at pH's that exceeded the ground state pKa of the chromophore where the conjugate base is the predominant form. Otherwise, substituents have only a very modest effect on the photoreaction of these robust chromophores.