Sumii Y, et al. Organic Letters, 2021, 23(7), 2777-2782
In this study, sodium difluoromethanesulfinate (HCF₂SO₂Na) was employed as a key reagent for the direct difluoromethanesulfinylation of alcohols, enabling the efficient synthesis of difluoromethanesulfinate esters. The reaction was conducted under mild conditions by treating a variety of primary, secondary, and tertiary alcohols with HCF₂SO₂Na in the presence of diphenylphosphoryl chloride (Ph₂P(O)Cl). This approach afforded the corresponding esters in good to excellent yields, demonstrating broad substrate tolerance. Furthermore, the methodology was successfully applied to the late-stage functionalization of complex, biologically active natural products, highlighting its synthetic versatility. The protocol was further adapted for trifluoromethanesulfinylation by utilizing CF₃SO₂Na with a catalytic amount of trimethylsilyl chloride (Me₃SiCl), providing access to trifluoromethanesulfinate esters.
