Transition‐Metal‐Free Trifluoromethylthiolation of N‐Heteroarenes

A general and efficient methodology for the direct transition metal free trifluoromethylthiolation of a broad range of biologically relevant N‐heteroarenes is reported employing abundant sodium chloride as the catalyst. This method is operationally simple, exhibits high functional group tolerance, and does not require protecting groups.     

Recent Advances and Perspectives of Transition Metal‐Catalyzed Asymmetric Fluorination Reactions

The synthesis of fluorine‐containing molecules has received intensive attention in recent years due to the great value of fluorides, however, the transition metal‐catalyzed asymmetric construction of C—F bonds is much less developed. This review presents the recent advancement of transition metal‐catalyzed asymmetric fluorination reactions, in which the final C—F bond is from reductive elimination of organometallic complexes. In addition, the perspective of the field is also provided for the future studies of asymmetric fluorinations and the related transformations, such as trifluoromethylation, trifluoromethylthiolation and trifluoromethoxylation.     

Copper–Boxmi Complexes as Highly Enantioselective Catalysts for Electrophilic Trifluoromethylthiolations

The enantioselective trifluoromethylthiolation of β‐ketoesters using chiral copper–boxmi complexes as catalysts is reported. A number of α‐SCF₃‐substituted β‐ketoesters have been obtained with up to >99 % enantiomeric excess (ee), and the trifluoromethylthiolated products were then transformed diastereoselectively to α‐SCF₃‐β‐hydroxyesters with two adjacent quaternary stereocenters.     

Silver‐Catalyzed Decarboxylative Trifluoromethylthiolation of Aliphatic Carboxylic Acids in Aqueous Emulsion

A silver‐catalyzed decarboxylative trifluoromethylthiolation of secondary and tertiary carboxylic acids under mild conditions tolerates a wide range of functional groups. The reaction was dramatically accelerated by its performance in an aqueous emulsion, which was formed by the addition of sodium dodecyl sulfate to water. It was proposed that the radical, which was generated from the silver‐catalyzed decarboxylation in the “oil‐in‐water” droplets, could easily react with the trifluoromethylthiolating reagent to form the product.     

One-Pot Regioselective γ-Trifluoromethylthiolation and γ-Methylthiolation of Enals

We describe herein the direct electrophilic γ-trifluoromethylthiolation and γ-methylthiolation of enals, via the in situ formation of the corresponding silyl dienol ether. This one-pot process is carried out under simple and mild reaction conditions and is compatible with a variety of functional groups.     

Synergistic Catalysis for the Umpolung Trifluoromethylthiolation of Tertiary Ethers

The first transition‐metal‐free, site‐specific umpolung trifluoromethylthiolation of tertiary alkyl ethers has been developed, achieving the challenging tertiary C(sp³)–SCF₃ coupling under redox‐neutral conditions. The synergism of organophotocatalyst 4CzIPN and BINOL‐based phosphorothiols can site‐selectively cleave tertiary sp³ C(sp³)–O ether bonds in complex molecules initiated by a polarity‐matching hydrogen‐atom‐transfer (HAT) event. The incorporation of several competing benzylic and methine C(sp³)?H bonds in alkyl ethers has little influence on the regioselectivity. Selective difluoromethylthiolation of C?O bonds has also been achieved. This represents not only an important step forward in trifluoromethylthiolation but also a promising means for site‐selective C?O bond functionalization of unsymmetrical tertiary alkyl ethers.