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.

Asymmetric Electrophilic Difluoromethylthiolation of Indanone-Based β-Keto Esters Using Difluoromethanesulfonyl Hypervalent Iodonium Ylides.

The first electrophilic diastereoselective direct introduction of the difluoromethylthio group is described. We used a chiral auxiliary-based approach to illustrate the versatility of our recently developed difluoromethanesulfonyl hypervalent iodonium ylide reagents for the difluoromethylthiolation of indanone-based β-keto esters. Chiral SCF₂H-featuring compounds were obtained in up to 93% ee value.

Difluoromethylthiolation of Phenols and Related Compounds with a HFCSONa/PhPCl/MeSiCl System.

A novel HFCSONa/PhPCl/MeSiCl system is disclosed for the late-stage direct difluoromethylthiolation of C and C nucleophiles. Difluoromethylthiolation of phenols and naphthols proceeded nicely under this system to regioselectively provide corresponding SCFH compounds in good yields. Other substrates such as indoles, pyrroles, pyrazoles, enamines, ketones, and β-keto esters were also transformed to corresponding SCFH products in good yields.

Synthesis of chiral (tetrazolyl)methyl-containing acrylates via silicon-induced organocatalytic kinetic resolution of Morita-Baylis-Hillman fluorides.

Reported herein is a new approach for the asymmetric installation of a (tetrazolyl)methyl group via Si/F activation using organocatalytic kinetic resolution of racemic MBH-fluorides.

Difluoromethanesulfonyl hypervalent iodonium ylides for electrophilic difluoromethylthiolation reactions under copper catalysis.

Difluoromethanesulfonyl hypervalent iodonium ylides 2 were developed as electrophilic difluoromethylthiolation reagents for a wide range of nucleophiles. Enamines, indoles, β-keto esters, silyl enol ethers and pyrroles were effectively reacted with 2 affording desired difluoromethylthio (SCF2H)-substituted compounds in good to high yields under copper catalysis. The reaction of allyl alcohols with 2 under the same conditions provided difluoromethylsulfinyl (S(O)CF2H) products in good yields.