Nickel-catalyzed asymmetric reductive arylation of α-chlorosulfones with aryl halides

Abstract

We report an asymmetric Ni-catalyzed reductive cross-coupling of aryl/ heteroaryl halides with racemic α-chlorosulfones to afford enantioenriched sulfones. The reaction tolerates a variety of functional groups under mild reaction conditions...

Nickel-Catalyzed Reductive Cross-Couplings: New Opportunities for Carbon–Carbon Bond Formations through Photochemistry and Electrochemistry

“…145 In this context, Reisman and co-workers 146 developed several enantioconvergent cross-coupling of racemic alkyl electrophiles in the presence of stoichiometric amounts of metallic reducing agents, including acylation, vinylation, arylation of racemic benzylic chlorides, and arylation of racemic α-chloronitriles. [147][148][149][150][151][152] These results led to the further development of the arylation of α-chlorosulfones, αchloroesters, and trifluoromethylated alkyl bromide by the research groups of Gong, 153 Reisman, 154 and Wang. 155 Mechanistically, enantioconvergence is achieved via the activation of an alkyl electrophile to form the alkyl radical (Scheme 17a).…”

Electrocatalytic synthesis: an environmentally benign alternative for radical-mediated aryl/alkenyl C(sp2)–C(sp3) cross-coupling reactions

“…In recent years, nickel-catalyzed asymmetric cross-coupling reactions have developed rapidly, 76 but electrochemically driven asymmetric electrophilic coupling reactions are rarely reported. In 2019, Reisman et al developed an appealing electrochemically enabled nickel-catalyzed asymmetric cross-coupling of alkenyl halides with benzyl halides to furnish 1,2-disubstituted alkenes bearing an allylic stereogenic center with excellent enantioselectivity in an undivided cell (Scheme 49).…”

Mechanistic views and computational studies on transition-metal-catalyzed reductive coupling reactions

“…The introduction of transition metal catalysis via selectively activating the corresponding electrophiles or stabilizing certain intermediates can effectively improve the yields and selectivity of reductive coupling reactions. 61–68 Semmelhack, Kende, and Kumada demonstrated the ability of Ni to mediate the reductive homocoupling of C(sp 2 ) halide electrophiles to construct biaryl products (Scheme 2(a)). 69–71 Many new reactions have been discovered based on different kinds of transition-metal insertions into various C–X (X: F, Cl, Br, I, OTf, etc. )…”