Transition‐metal catalyzed intermolecular 1,2‐diarylation of electronically unactivated alkenes has emerged as an extensive research topic in organic synthesis. However, most examples are mainly limited to terminal alkenes. Furthermore, transition‐metal catalyzed asymmetric 1,2‐diarylation of unactivated alkenes still remains unsolved and is a formidable challenge. Herein, we describe a highly efficient directed nickel‐catalyzed reductive 1,2‐diarylation of unactivated internal alkenes with high diastereoselectivities. More importantly, our further effort towards enantioselective 1,2‐diarylation of the unactivated terminal and challenging internal alkenes is achieved, furnishing various polyarylalkanes featuring benzylic stereocenters in high yields and with good to high enantioselectivities and high diastereoselectivities. Interestingly, the generation of cationic Ni‐catalyst by adding alkali metal fluoride is the key to increased efficiency of this enantioselective reaction.

Transition-metal catalyzed intermolecular 1,2diarylation of electronically unactivated alkenes has emerged as an extensive research topic in organic synthesis. However, most examples are mainly limited to terminal alkenes. Furthermore, transition-metal catalyzed asymmetric 1,2-diarylation of unactivated alkenes still remains unsolved and is a formidable challenge. Herein, we describe a highly efficient directed nickelcatalyzed reductive 1,2-diarylation of unactivated internal alkenes with high diastereoselectivities. More importantly, our further effort towards enantioselective 1,2diarylation of the unactivated terminal and challenging internal alkenes is achieved, furnishing various polyarylalkanes featuring benzylic stereocenters in high yields and with good to high enantioselectivities and high diastereoselectivities. Interestingly, the generation of cationic Ni-catalyst by adding alkali metal fluoride is the key to increased efficiency of this enantioselective reaction.

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Asymmetric multicomponent reactions are considered as efficient protocols for constructing complex chiral molecules because of their step‐ and atom‐economy. Nickel‐catalyzed asymmetric three‐component dicarbofunctionalization of alkenes has been well developed in recent years, which is used in the area of total synthesis of natural products and late‐stage modification of drugs because of the rapid incorporation of chiral sp3‐enriched carbon centers. In this concept, the significant breakthroughs of this field are summarized, together with the related mechanisms. Moreover, the remaining challenges and potential opportunities of multicomponent dicarbofunctionalization are also highlighted.

Transition metal‐catalyzed C−S cross‐coupling has emerged as an important strategy to furnish thioethers; however, the dominant utilization of noble metal catalysts as well as the construction of challenging C(sp3)−S bonds by transition metal‐catalysis remain highly problematic. Earth‐abundant manganese has gathered increasing interest as an attractive catalyst for new reaction development; nevertheless, C(sp3)−S cross‐coupling reaction by manganese catalysis has not been reported. Herein, we disclose a highly efficient manganese‐catalyzed redox‐neutral thiolation of a broad range of alkyl halides with thioformates as practical sulfuration agents. Strategically, employing easily synthesized thioformates as thiyl radical precursors allows access to various aryl and alkyl thioethers in good to excellent yields. Notably, this redox‐neutral method avoids the utilization of strong bases, external ligands, forcing reaction conditions, and stoichiometric manganese, thus presenting apparent advantages, such as broad substrate scope, excellent functional group compatibility, and mild reaction conditions. Finally, the utilities of this method are also illustrated by downstream transformations and late‐stage thiolation of structurally complex natural products and pharmaceuticals.