Synthesis of Difluoromethanesulfinate Esters by the Difluoromethanesulfinylation of Alcohols.

Herein, we report the first synthesis of difluoromethanesulfinate esters via the direct difluoromethanesulfinylation of alcohols with HCFSONa/PhP(O)Cl. Primary, secondary, and tertiary alcohols were converted to the corresponding difluoromethanesulfinate esters in good to excellent yields under mild conditions. The late-stage functionalization of complexed biologically active natural products was also demonstrated. The method was extended to the trifluoromethanesulfinylation of alcohols using CFSONa in the presence of a catalytic amount of MeSiCl to provide trifluoromethanesulfinate esters.