Functionalized 1,2-Dioxetanes as Potential Phototherapeutic Agents: The Synthesis of Carboxylate, Carbonate, Carbamate, and Ether Derivatives of 3-(Hydroxymethyl)-3,4,4-trimethyl-1,2-dioxetane

Article abstract of DOI:10.1021/jo00390a018

With gentle and efficient synthetic methods, 3-(hydroxymethyl)-3,4,4-trimethyl-1,2-dioxetane (1) can be transformed with appropriate electrophiles in moderate to good yields into functionalized derivatives of dioxetane 1.As electrophiles served carboxylic acids, chlorocarbonates, isocyanates, trialkyloxonium salts, and trialkylsilyl chlorides.With 1 these afford respectively dioxetanes with carboxylate, carbonate, carbamate, ether, and silyl ether functionalities.Nucleophilic activation of the hydroxymethyl substituent in the dioxetane 1 can be achieved under mild conditions by pyridine, 4-(dimethylamino)pyridine, potassium hydride, or butyllithium.Such functionalized dioxetanes serve as chemical sources of triplet excited carbonyl compounds which should find interesting utilization in photobiology and photomedicine, e.g. as potential phototherapeutic agents