Chiral phosphine-containing skeletons are important motifs in bioactive natural products, pharmaceuticals, chiral catalysts, and ligands. Herein, we report a general and modular platform to access chiral α-aryl phosphorus compounds via a Ni/photoredox-catalyzed enantioconvergent reductive cross-coupling between α-bromophosphates and aryl iodides. This dual catalytic regime exhibited high efficiency and good functional group compacity. A wide variety of substrates bearing a diverse set of functional groups could be converted into chiral phosphates in good to excellent yields and enantioselectivities. The utility of the method was also demonstrated by the development of a new phosphine ligand and the synthesis of enzyme inhibitor derivatives. The detailed mechanistic studies supported a radical chain process and revealed a unique distinction compared with traditional reductive cross-coupling.

The flourishing Ni/photoredox-catalyzed asymmetric couplings typically rely on redox-neutral reactions. In this work, we report a reductive cross-coupling of aryl iodides and α-chloroboranes under a dual catalytic regime to further enrich the metallaphotoredox chemistry. This approach proceeds under mild conditions (visible light, ambient temperature, no strong base) to access the versatile benzylic boronic esters with good functional group tolerance and excellent enantioselectivities.

Deoxygenative difunctionalization of carbonyls represents a convenient route to construct complex molecules considering the readily available aldehyde and ketone compounds. The present approaches typically rely on strategies via carbene, carbanion, or carbocation equivalents. Herein, combined with dual nickel/photoredox catalysis regime, we developed a strategy through a radical intermediate to achieve the deoxygenative arylboration of aldehydes. Compared with the known patterns of carbon−oxygen (C−O) bond transformations, this coupling of C-OBPin unit opens a direction for this chemistry. A wide variety of substrates bearing a diverse set of functional groups were compatible with this method under very mild conditions (visible light, ambient temperature, no strong base) to afford the benzylic boronic esters, which have important versatilities in organic synthesis.

Transition-metal-catalyzed asymmetric carbonÀ carbon bond formation to forge phosphonates with an α-chiral carbon center through C(sp 3 )À C(sp 3 ) and C(sp 2 )À C(sp 3 ) couplings has been successful. However, the enantioselective C(sp)À C(sp 3 ) coupling has not yet been disclosed. Reported herein is an unprecedented enantioconvergent cross-coupling of alkynyl bromides and α-bromo phosphonates to deliver chiral α-alkynyl phosphonates.

Transition‐metal‐catalyzed asymmetric carbon−carbon bond formation to forge phosphonates with an α‐chiral carbon center through C(sp3)−C(sp3) and C(sp2)−C(sp3) couplings has been successful. However, the enantioselective C(sp)−C(sp3) coupling has not yet been disclosed. Reported herein is an unprecedented enantioconvergent cross‐coupling of alkynyl bromides and α‐bromo phosphonates to deliver chiral α‐alkynyl phosphonates.