Trifluoromethanesulfinyl Chloride for Electrophilic Trifluoromethythiolation and Bifunctional Chlorotrifluoromethythiolation

• Published in: Chemistry : a European journal Vol. 24; no. 70; pp. 18749 - 18756
• Main Authors: Jiang, Lvqi, Yan, Qiang, Wang, Rongkang, Ding, Tianqi, Yi, Wenbin, Zhang, Wei
• Format: Journal Article
• Language: English
• Published: WEINHEIM Wiley 12.12.2018; Wiley Subscription Services, Inc
• Subjects: Chemistry; Chemistry, Multidisciplinary; Chlorides; chlorotrifluoromethythiolation; Disproportionation; Indoles; Ketones; organic chemistry; Physical Sciences; Reagents; Science & Technology; Styrenes; Thiols; Thiophenes; trifluoromethanesulfinyl chloride; trifluoromethythiolation; SODIUM TRIFLUOROMETHANESULFINATE; trifluoromethythiolation; IODONIUM YLIDE; COCCIDIOSIS; TOLTRAZURIL; DIFLUOROMETHYLTHIOLATION; ketones; trifluoromethanesulfinyl chloride; PERFLUOROALKYLTHIOLATION; INDOLES; organic chemistry; chlorotrifluoromethythiolation; HYPERVALENT IODINE REAGENT; CF3SO2NA; FREE DIRECT TRIFLUOROMETHYLTHIOLATION
• ISSN: 0947-6539; 1521-3765
• DOI: 10.1002/chem.201804027

Trifluoromethanesulfinyl chloride (CF3SOCl) has been introduced as a new reagent for C−H trifluoromethylthiolation of indoles, thiophenes, and ketones under catalyst‐free conditions and in the absence of reductant. The disproportionation of CF3SOCl to CF3SO2Cl and CF3SCl provides two pathways for the trifluoromethylthiolation. Direct trifluoromethylthiolation with CF3SCl or trifluoromethylsulfoxidation with CF3SOCl is followed by reduction with CF3SOCl. This reagent can be used to functionalize benzothiophenes, benzofurans, and indenes under the promotion of Ag2CO3. It can also be used for trifluoromethylthiolation of thiols and benzeneselenols, and 1,2‐bifunctional chlorotrifluoromethylthiolation of indoles, styrenes, and alkyenes. The method can also be extended for difluorometylthiolation reactions using CF2HSOCl. Synthesis: Trifluoromethanesulfinyl chloride (CF3SOCl) has been introduced as a new reagent for the C−H trifluoromethylthiolation of indoles, thiophenes, ketones, thiols, and benzeneselenols, as well as 1,2‐chlorotrifluoromethylthiolation of indoles, styrenes, and alkyenes (see scheme).