35896-45-8Relevant academic research and scientific papers
Synthesis of Difluoromethanesulfinate Esters by the Difluoromethanesulfinylation of Alcohols
Sumii, Yuji,Sasaki, Kenta,Matsubara, Okiya,Shibata, Norio
supporting information, p. 2777 - 2782 (2021/04/12)
Herein, we report the first synthesis of difluoromethanesulfinate esters via the direct difluoromethanesulfinylation of alcohols with HCF2SO2Na/Ph2P(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 CF3SO2Na in the presence of a catalytic amount of Me3SiCl to provide trifluoromethanesulfinate esters.
THE SYNTHESIS, SOLVOLYSIS AND REARRANGEMENT OF BENZYL TRIFLUOROMETHANESULFINATES
Braverman, Samuel,Manor, Haim
, p. 357 - 365 (2007/10/02)
The synthesis and reactivity of benzyl trifluoromethanesulfinates have been investigated.These esters are easily and almost quantitatively obtained by selective oxidation of the corresponding sulfenates.A study of their behavior has revealed some unique features.In sharp contrast to benzyl arenesulfinates, which undergo ethanolysis with complete sulfur-oxygen bond fission, the corresponding trifluoromethanesulfinates undergo ethanolysis with exclusive carbon-oxygen bond fission, and with a rate enhancement by a factor of 6 powers of ten.The unusual high reactivity of these esters, comparable to that of the corresponding tosylates, is discussed.A kinetic study of the solvent and substituents effects on the rate of solvolysis has been performed.Also in contrast with benzyl arenesulfinates, these esters undergo facile rearrangement to sulfone on heating in polar nonhydroxylic solvents such as acetonitrile, in high yields.The mechanisms of solvolysis and rearrangement are discussed.
