A Ni-catalyzed enantioselective reductive diarylation of activated alkenes by domino cyclizative/cross-coupling of two aryl bromides is developed. This reaction proceeds under very mild conditions and shows broad substrate scope, without requiring the use of preformed organometallic reagents. Moreover, this approach provides direct access to various bis-heterocycles bearing all-carbon quaternary centers in synthetically useful yields (up to 81%) with excellent enantioselectivity (>30 examples, 90–99% ee).

The first nickel-catalyzed domino Heck cyclization/Suzuki coupling reaction for the synthesis of 3,3-disubstituted oxindoles bearing quaternary all-carbon centers is reported. A wide range of electrophiles, such as aryl iodides, bromides, triflates, and chlorides, are all compatible with the reaction conditions. Moreover, cheap aryl esters, which undergo catalytic C-O bond cleavage, could also be employed as electrophiles. The approach shows good yields and broad scope, complementing a more practical and sustainable alternative to the conventional palladium-based analogues.

Transition-metal-catalytic domino reactions represent important advances in synthetic organic chemistry. Their development benefits synthesis by providing highly efficient and step-economical methods to complex molecules with impressive selectivity. Herein, a Ni-catalyzed domino reductive cyclization of acrylamides with alkynyl bromides is reported, enabling rapid assembly of a range of substituted 2,3-fused cyclopentannulated indolines. Preliminary mechanistic studies revealed that tricyclic indolines are afforded through a highly regioselective migratory insertion of 1,3-diynes, which are formed from the homocoupling of alkynyl bromides, into the in situ generated σ-alkyl-Ni­(II) species, followed by nucleophilic addition of the resulting alkenyl nickel to unactivated amides. Most importantly, a highly regio- and enantioselective reductive cyclization of acrylamides and internal alkynes has also been developed. This transformation takes place under mild conditions with high efficiency, providing a rapid access to structurally diverse cyclopentannulated indolines in synthetically useful yields with high regioselectivity (>20/1) and enantioselectivity (27 examples, 82–96% ee).

A highly regioselective [2 + 2 + 2] cyclization of aromatic alkynes with nitriles is developed for the preparation of 2,3,6-trisubstituted pyridines under visible-light irradiation using a pyrylium salt as the photoredox catalyst. This cycloaddition is achieved through a photooxidative single-electron-transfer process at room temperature and under metal-free conditions. A variety of aromatic alkynes and nitriles are employed to furnish the annulation products in good yields.

Highly efficient (n)Bu3P-catalyzed desulfonylative [3 + 2] cycloadditions of allylic carbonates with arylazosulfones were developed for the synthesis of pyrazole derivatives. The reactions proceed smoothly under mild conditions to generate corresponding annulation products in good to excellent yields.

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A direct synthesis of 4-aryltetralones from aromatic alkenes and O2 using acridinium as the photocatalyst under visible light irradiation was developed.

Control of enantioselectivity in radical reactions was a formidable challenge for organic chemists for decades. Thanks to the key role of transition metal complexes both in promoting and highly enantioselectively controlling sophisticated synthetic routes, great improvements in this filed have been achieved by merging transition‐metal asymmetric catalysis with radical chemistry. Herein we provide a perspective of some of the most significant contributions in the field during the past decades. Accordingly, the major advances are classified based on different strategies for controlling stereoselectivity including: (1) chiral metal complex chelation, (2) chiral metal complex combined with radical species and reductive elimination, (3) chiral metal complex outer‐sphere substitution by radical intermediate. Brief discussion of mechanism is presented whenever relevant.