Alkylation of Amino Acids and Glutathione in Water by o-Quinone Methide.Reactivity and Selectivity

o-Quinone methide (1) has been produced in water both thermally and photochemically from (2- hydroxybenzyl)trimethylammonium iodide (2). Michael addition reactions of 1 to various amines, and sulfides, including amino acids and glutathione have been carried out, obtaining alkylated adducts (3-16) in fairly good to quantitative yields. The reaction rate and selectivity of 1 toward nitrogen and sulfur nucleophiles, in competition with the hydration reaction, have been investigated at different pH by laser flash photolysis technique. Furthermore, several alkylation adducts regenerate 1 either by heating (9, 10, 13, and 14) or by irradiation (9, 11-13, 16). Such a thermal and photochemical reversibility of the alkylation process opens a new perspective for the use and application of such adducts as o-QM molecular carriers.