Lvqi Jiang

Direct Trifluoromethylthiolation and Perfluoroalkylthiolation of C(sp2)H Bonds with CF3SO2Na and RfSO2Na

A new method for CF3SO2Na-based direct trifluoromethylthiolation of C(sp(2))-H bonds has been developed. CF3SSCF3 is generated in situ from cheap and easy-to-handle CF3SO2Na, and in the presence of CuCl can be used for electrophilic trifluoromethylthiolation of indoles, pyrroles, and enamines. The method has been extended to perfluoroalkylthiolation reactions using RfSO2Na.

One-Pot Synthesis of Difluoromethyl Thioethers from Thiourea and Diethyl Bromodifluoromethylphosphonate

A straightforward one-pot synthesis of difluoromethyl thioethers from thiourea and diethyl bromodifluoromethylphosphonate has been developed. Thiourea is a cheap and friendly sulfur reagent, while diethyl bromodifluoromethylphosphonate is a low-cost and stable difluorocarbene precursor. The strategy enabled the introduction of SCF2H moieties into indoles, pyrroles, and activated arenes and formed a number of difluoromethyl thioethers.

Fluoroalkylsulfonyl Chlorides Promoted Vicinal Chloro-fluoroalkylthiolation of Alkenes and Alkynes

The unprecedented use of CF3SO2Cl for direct bifunctional chloro-trifluoromethylthiolation of alkenes and alkynes is reported. CF3SCl, which is generated by the reduction of PPh3, undergoes electrophilic addition and then chlorination to give the bifunctionalized products without using an additional chlorine source. The method is also applicable for chloro-difluoromethylthiolation using CF2HSO2Cl.

Metal-Free Electrophilic Trifluoroethylthiolation with NaSO2CH2CF3

Metal-free trifluoroethylthiolation with fluorinated sulfinate salt NaSO2CH2CF3 under reductive conditions has been developed. The strategy enables the installation of the SCH2CF3 moiety efficiently to form a number of unexplored stable trifluoroethylthiolated heterocycles, arenes, and thiols, which have the potential to be a new series of fluorine-containing chemical entities for medicinal chemists.

Bunte Salt CH2FSSO3Na: An Efficient and Odorless Reagent for Monofluoromethylthiolation

A practical and efficient monofluoromethylthiolation that employs the typical Bunte salt, sodium S-(fluoromethyl) sulfurothioate, as the sulfur source is described. This reagent reacts readily with a variety of aryl amines and aryl thiols. The high tolerance of functional groups demonstrates the potential of this reaction. In addition, this method is suitable for the late-stage monofluoromethylthiolation of complex bioactive molecules.

Copper-Catalyzed Vicinal Chloro-thiolation of Alkynes with Sulfonyl Chlorides

A copper-catalyzed vicinal chloro-thiolation of alkynes with inexpensive and diversified sulfonyl chlorides RSO2Cl (R = aryl, alkyl) has been developed. This practical and scalable reaction could be used for the construction of a number of unexplored bioactive chlorothiolated alkenes. Internal alkynes could also undergo the chloro-thiolation to provide tetrasubstituted alkynes. Preliminary mechanistic investigations revealed a plausible radical process involving a sulfur-centered radical intermediate via copper-mediated homolysis of the S-Cl bond.

Trifluoromethanesulfinyl Chloride for Electrophilic Trifluoromethythiolation and Bifunctional Chlorotrifluoromethythiolation

Trifluoromethanesulfinyl chloride (CF3 SOCl) 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 CF3 SOCl to CF3 SO2 Cl and CF3 SCl provides two pathways for the trifluoromethylthiolation. Direct trifluoromethylthiolation with CF3 SCl or trifluoromethylsulfoxidation with CF3 SOCl is followed by reduction with CF3 SOCl. This reagent can be used to functionalize benzothiophenes, benzofurans, and indenes under the promotion of Ag2 CO3 . 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 CF2 HSOCl.