Water-Mediated ortho-Carboxymethylation of Aryl Ketones under Ir(III)-Catalytic Conditions: Step Economy Total Synthesis of Cytosporones A-C.

An expeditious Ir(III)-catalyzed carboxymethylation of aryl ketone with diazotized Meldrum's acid has been developed in aqueous medium. Flavanone and chromanone were also found to be facile substrates with the developed catalytic system. Mechanistic studies revealed the active catalytic species and the role of water in the reaction process as hydroxy and proton sources. Employing the developed method, total synthesis of cytosporone A was achieved in two steps and that of cytosporones B-C was achieved in three steps starting from resorcinol.