Trifluoromethanesulfinyl Chloride for Electrophilic Trifluoromethythiolation and Bifunctional Chlorotrifluoromethythiolation

Abstract

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.

Novel Bifunctionalization of Activated Methylene: Base‐Promoted Trifluoromethylthiolation of β‐Diketones with Trifluoromethanesulfinyl Chloride

“…reported the trifluoromethylthiolation of ketones with CF 3 SOCl [Scheme , Eq. (2)] . In our continuous study on the development of trifluoromethylthiolation methods with easily available and cheap reagents, it was found that the trifluoromethylthiolation‐based bifunctionalization of β‐diketones could be achieved with CF 3 SOCl [Scheme , Eq.…”

“…Based on the experimental results and literature reports, a plausible mechanism was proposed for the above reactions as showed in Scheme . The reaction of 1 and base affords anion intermediate A , which reacts with CF 3 SOCl to give compound B .…”

“…Controle xperiments indicated that base was important for the reaction (entry 7). So we studied the base effect further.However,v arious organic bases, such as triethylamine (Et 3 N), triisopropylamine (iPr 3 N), N-methylpiperidine andp iperidine,c ould not improvet he yield of 2a (entries 8-11), and inorganic bases (Na 2 CO 3 ,K 2 CO 3 ,N aHCO 3 , NaOH, K 3 PO 4 )f ailed to promote this bifunctionalization reaction with full recovery of 1a (entries [12][13][14][15][16]. Therefore, pyridine was chosen as the base to further study the solvent effect.…”

“…Based on the experimental results and literaturer eports, [13,15,19] ap lausible mechanism was proposed for the above reactions as showed in Scheme6. In conclusion, we have demonstrated an ovel method for the trifluoromethylthiolation-based bifunctionalization of activated methylene with cheap and easily available trifluoromethylthiolating reagent.…”

Recent Progress on Direct Difluoromethylthiolation and Monofluoromethylthiolation

“…以 CuBr 为催化剂, 用含有手性萘胺的烯胺化合物与该 试剂在甲苯中室温反应, 可以中等的收率得到含有 SCF 2 H 的手性化合物, ee 值最高可达 93% (Scheme 4) [36] . [41] 在研究三氟甲基亚磺酰氯 [55] . 2016 年, Glorius 课题组 [56]…”