Deoxygenative Tri- and Difluoromethylthiolation of Carboxylic Acids with Benzothiazolium Reagents
Matteo Tironi, Lilian M. Maas, Arushi Garg, Stefan Dix, Jan P. Götze, Matthew N. Hopkinson
Abstract
Deoxygenative syntheses of fluorinated thioesters directly from carboxylic acids have been developed employing benzothiazolium reagents. The process using BT-SCF3 represents an attractive approach toward these SCF3-containing compounds that avoids the use of metal –SCF3 salts or preactivated acyl electrophiles. Moreover, the in situ activation of BT-SCF2H allows for an unprecedented nucleophilic difluoromethylthiolation reaction. DFT calculations support a mechanistic scenario involving a four-membered transition state where acyl substitution occurs without the formation of an unstable free –SCF2H anion.
Topics & Concepts
ChemistryReagentCarboxylic acidCombinatorial chemistryOrganic chemistryFluorine in Organic ChemistrySulfur-Based Synthesis TechniquesSynthesis and Reactions of Organic Compounds