The Study of Sulfenate and Sterically Hindered Chalcogenide Anions as Organocatalysts for the Construction of C-C Bonds

Chalcogenides are highly redox active and biologically potent nucleophiles with significant unexplored catalytic potential. In particular, sulfenate anions potential as organocatalyst has largely been overlooked in the literature due to their esoteric status. A unique sulfenate anion catalyzed Baylis Hillman (BH) reaction forming sp2-sp3 C-C bonds is in development. In this two-part study, part one focuses on screening conditions suitable for both cleavage of a precatalyst and subsequent BH reaction. Whereas part two focuses on the proclivity of chalcogenide oxyanions to disproportionate. Sterically hindered analogs were investigated, to prevent catalyst decomposition. The sulfenate anion catalyzed (20 mol %) BH reaction was conducted in the presence of α,β-unsaturated nitriles, ketones and esters to generate allylic alcohols in yields up to 37%. Precatalyst cleavage studies were an integral part to the realization of smooth sulfenate anion generation. Efforts to optimize the BH reaction conditions are ongoing.