Rh(ii)/phosphine-cocatalyzed synthesis of dithioketal derivatives from diazo compounds through simultaneous construction of two different C–S bonds

Abstract

Rhodium(II)/phosphine-cocatalyzed bis-sulfuration of α-diazocarbonyl compounds using thiosulfonates as the sulfenylating agent, which provided two sulfur-containing moieties, was developed via simultaneous inter- and intra-molecular C–S bond formation. This novel protocol provides a rapid synthetic route to dithioketal derivatives in moderate to good yields in an atom-economic process. The transformation is proposed to proceed through phosphine ylide formation followed by S(O₂)–S bond cleavage and rearrangement.