Asymmetric -Selective Borylalkylation of Terminal Alkynes by Nickel Catalysis.

Selective transformation of alkyne triple bonds to double bonds serves as an efficient platform to construct substituted alkenes. While significant advances have been made in its spatiotemporal regulation, achieving a multicomponent enantioselective reaction that requires multifaceted selectivity issues to be overcome is still uncommon. Here, we report an unprecedented asymmetric -stereoselective borylcarbofunctionalization of terminal alkynes by nickel catalysis.

Fe-S Catalyst Generated In Situ from Fe(III)- and S-Promoted Aerobic Oxidation of Terminal Alkenes.

An iron-sulfur complex formed by the simple mixture of FeCl with S generated in situ from KS is developed and applied to selective aerobic oxidation of terminal alkenes. The reaction was carried out under an atmosphere of O (balloon) and could proceed on a gram scale, expanding the application of S in organic synthesis. This study also encourages us to explore the application of an Fe-S catalyst in organic reactions.

Transition-Metal-Free Decarboxylative Cyclization of -Arylacrylamides with 2,2-Difluoro-2-(phenylthio)acetic Acid: Synthesis of Thiodifluorooxindole Derivatives.

An efficient transition-metal-free decarboxylative cyclization of -arylacrylamides with 2,2-difluoro-2-(phenylthio)acetic acid for the construction of thiodifluoroindoleone derivatives is described. This strategy features stable and readily available substrates, mild reaction conditions, and transition-metal-free catalysts. Notably, this protocol has successfully applied to synthesis of -difluoroalkenes, which exist in numerous biologically active compounds.

Visible-Light-Promoted Cross-Coupling Reactions of Aryldiazonium Salts with -Methyl- Sulfonothioate or -Methyl- Selenium Sulfonate: Synthesis of Trideuteromethylated Sulfides, Sulfoxides, and Selenides.

A novel visible-light-photocatalytic deuterated thiomethylation/methylselenation of aryldiazonium salts utilizing /methyl- sulfonothioate has been developed. The mild conditions and the various functional groups provide a green protocol for the efficient and rapid introduction of the -CD or -CD group with useful levels of deuterium content (>91% D). Trideuteromethyl sulfoxides have also been successfully chemoselectively observed by simple atmospheric changes under photocatalytic conditions.