Catalytic three-component dicarbofunctionalization reactions involving radical capture by nickel

Abstract

In this review, we summarize the recent advances in the area of catalytic dicarbofunctionalization of unsaturated π bonds by underpinning the catalytic domino transformations involving radical capture by nickel.

Photo‐Catalyzed Redox‐Neutral 1,2‐Dialkylation of Alkenes

“…On the basis of the above results and previous reports, [2g,6a,9a,l–n,10a,11a,16] we proposed a plausible reaction pathway as depicted in Scheme 3. Under the irradiation of blue light, cesium oxalate 1 was oxidized by photoexcited catalyst *Ir(III) followed by double decarboxylation to generate the nucleophilic tertiary alkyl radical 4 and the reduced photocatalyst Ir(II).…”

“…The visible light catalysis, characterized by its unique redox properties and mild reaction mode, has become an important research field of catalytic organic synthesis [4] . The merger of photoredox and transition‐ metal catalysis has greatly expanded the scope of dicarbofunctionalization of alkenes [2g,h,5] . However, only a handful of reports dealing with the three‐component 1,2‐dialkylation of alkenes under photoredox catalysis have been reported to date [6] .…”

N-Heterocyclic Carbene-Catalyzed 1,4-Alkylacylation of 1,3-Enynes

“…With the recent renaissance in radical chemistry, direct difunctionalization of olefins has become a general strategy for introducing functional groups and chain branches onto unsaturated hydrocarbon feedstocks . An anti-Markovnikov radical addition to an olefin leads to the formation of a carbon radical that can be incepted by another polarity-matching radical via radical–radical coupling − or undergo transition-metal-mediated redox coupling reaction .…”

Three-Component Visible-Light-Induced Palladium-Catalyzed 1,2-Alkyl Carbamoylation/Cyanation of Alkenes

“…The multicomponent 1,2-difunctionalization of alkenes is a valuable synthetic strategy that allows for an efficient construction of complex molecules in a single step from easily accessible and commercially available starting materials (Scheme a) . Particularly attractive could be the 1,2-alkyl carbamoylation of alkenes, which would enable access to synthetically important amides, the prevalent structural motifs found in pharmaceuticals, biological molecules, and polymeric materials .…”