In contrast, the two-component enantioselective cross-coupling of sp 3 -hybridized electrophiles with various arylation reagents, which is catalyzed by transition metals such as nickel, cobalt, and iron, has emerged as a powerful alternative, particularly for the construction of challenging C(sp 3 )-C(sp 2 ) bonds. Representative strategies include Fu's seminal studies on the Ni-catalyzed asymmetric Negishi arylation of alkyl electrophiles, 5 in addition to the Ni-, Co-, and Fe-catalyzed Kumada arylation of α-bromoketones, α-bromo esters, and α-chloroesters that have been independently reported by Fu, Zhong/Bian, and Nakamura (Figure ). Alternatively, the Ni-catalyzed enantioselective reductive cross-electrophile coupling provides a promising paradigm for arylation of sp 3 -hybridized electrophiles by using another electrophilic aryl halides, in the presence of stoichiometric organic or metal reductants, and thereby circumventing the use of sensitive organometallic reagents. A range of studies from Doyle, Wang, Lei/Gong, Reisman, 9b Shi, 9c and Wang 9d demonstrate that styrenyl aziridines, CF3-substituted alkyl bromides, α-chlorosulfones, α-chloroesters, benzylic chlorides, and propargylic chlorides undergo chiral nickel/bisoxazoline-catalyzed asymmetric cross-electrophile couplings to afford the chiral arylated products with high enantioselectivity (Figure 1B, b). Moreover, Doyle 10a and Mei 10b have successfully merged asymmetric nickel catalysis with photoredox catalysis or paired electrolysis to provide milder enantioselective reductive crosscoupling processes for the arylation of styrene oxides and α-chloroesters. It has been accepted that many of these Ni-catalyzed cross-coupling processes of alkyl halides involve oxidative addition via a radical mechanism. This unique blueprint lays the foundation for the development of an asymmetric three-component arylative cross-coupling of alkenes using aryl bromides or two distinct Csp 2and Csp 3 -halides, as demonstrated by elegant recent examples independently reported by Diao, Nevado, and Pioneered by Molander and MacMillan, many groups have reported a range of redox-active precursors that are amenable to single-electron-transfer (SET) oxidation to form alkyl carbon radicals, which serve as formal nucleophiles to participate in two- and three-component 15 arylative radical cross-couplings under synergistic photoredox and nickel catalysis (Figure 1B, c). Owing to the redox-neutral conditions, these approaches provide wider substrate scope for the construction of diverse chiral molecules that feature (hetero)aryl-substituted stereogenic centers without the necessity for an external reductant. Consequently, a range of groups have reported the asymmetric copper-catalyzed cross-couplings of readily available and stable aryl boronic acids, organoboronate esters and azoles with benzylic radicals and α-amide radicals derived from alkylarenes, benzylic halides, or Katritzky salts (Figure , d). These two-component Suzuki-Miyaura-type radical cross-couplings provide access to a wide range of valuable enantioenriched compounds bearing (hetero)aryl-substituted stereocenters in a mild and efficient manner. In an adaptation to this approach, several groups have recently disclosed a range of three-component variants using styrene derivatives, α-substituted acrylamides, N-vinylbenzamides, and tert-butyl acrylate to relay the initially formed carbon radicals. 17 Remarkably, Liu, G., Maruoka, 17e and Zhang 17f have achieved outstanding examples of copper-catalyzed highly enantioselective three-component asymmetric (hetero)arylative radical cross-couplings of vinylarenes or α-substituted acrylamides. Quite recently, Nevado 17g and Mei 17h independently reported nickel-catalyzed three-component asymmetric arylative radical cross-couplings of N-vinylbenzamides and tert-butyl acrylates under photochemical or electrochemical conditions.