Driven by the continuous demand for optically active fluoro-containing molecules from the chemical society, the field of fluorochemistry has emerged as a hot topic recently. While protocols focusing on catalytic asymmetric fluorination, (di)fluoroalkylation, and trifluoromethylation have been well developed, elegant strategies for the synthesis of enantioenriched monofluoro- and gem-difluoroalkenes remain highly sought after. As two vital subunits of organofluorides, both monofluoro- and gem-difluoroalkenes are pervasive within many biologically active molecules. They serve as the mimics of alkenyl, enol, and peptide bonds and the carbonyl group, respectively, which may enhance the bioactivities of the parent molecules. In addition, they are active handles for the construction of other fluorinated molecules. In this review, insightful discussions on the latest achievements of the catalytic asymmetric strategies associated with the facile synthesis of both monofluoro- and gem-difluoroalkenes are provided. The related mechanism considerations, applications in streamlining syntheses, limitations, and the opportunities of the state-of-the-art methodologies will be highlighted. We hope that this will trigger novel ideas, helping in pushing current frontiers further.

Organofluorine compounds are of high value. NHC-catalyzed fluorination and fluoroalkylation have served as powerful and versatile vehicles for accessing the related organofluorines. This review focuses on the recent developments in this area.

The catalytic asymmetric dearomatization (CADA) reaction has proved to be a powerful protocol for rapid assembly of valuable three-dimensional cyclic compounds from readily available planar aromatics. In contrast to the well-studied indoles and naphthols, phenols have been considered challenging substrates for intermolecular CADA reactions due to the combination of strong aromaticity and potential regioselectivity issue over the multiple nucleophilic sites (O, C2 as well as C4). Reported herein are the chiral phosphoric acid-catalyzed divergent intermolecular CADA reactions of common phenols with azoalkenes, which deliver the tetrahydroindolone and cyclohexadienone products bearing an all-carbon quaternary stereogenic center in good yields with excellent ee values. Notably, simply adjusting the reaction temperature leads to the chemo-divergent intermolecular (3 + 2) and alkylation dearomatization reactions. Moreover, the stereo-divergent synthesis of four possible stereoisomers in a kind has been achieved via changing the sequence of catalyst enantiomers.

We report a method for the synthesis of a universal deuterated methylthiolating reagent through a one-pot gram-scale operation under mild conditions. This reacts with various nucleophiles to give SCD3 analogues with high deuterium levels (>99% D).