1,2-Dicarbofunctionalization of alkenes has emerged as an efficient synthetic strategy for preparing substituted molecules by coupling readily available alkenes with electrophiles and/or nucleophiles Nickel complexes serve as effective catalysts owing to their tendency to undergo facile oxidative addition and slow β-hydride elimination, and their capability to access both two-electron and radical pathways Two-component alkene functionalization reactions have achieved high chemo-, regio-, and stereoselectivities by tethering one of the coupling partners to the alkene substrate Three-component reactions, however, often incorporate directing groups to control the selectivity Only a few examples of directing-group-free difunctionalizations of unactivated alkenes have been reported Therefore, great opportunities exist for the development of three-component difunctionalization reactions with broad substrate scopes and tunable chemo-, regio-, and stereoselectivities

Nickel-Catalyzed Dicarbofunctionalization of Alkenes

The first Suzuki cross-couplings of unactivated tertiary alkyl electrophiles are described. The method employs a readily accessible catalyst (NiBr2·diglyme/4,4′-di-tert-butyl-2,2′-bipyridine, both commercially available) and represents the initial example of the use of a group 10 catalyst to cross-couple unactivated tertiary electrophiles to form C–C bonds. This approach to the synthesis of all-carbon quaternary carbon centers does not suffer from isomerization of the alkyl group, in contrast with the umpolung strategy for this bond construction (cross-coupling of a tertiary alkylmetal with an aryl electrophile). Preliminary mechanistic studies are consistent with the generation of a radical intermediate along the reaction pathway.

Nickel-Catalyzed Carbon–Carbon Bond-Forming Reactions of Unactivated Tertiary Alkyl Halides: Suzuki Arylations

Substantial advances in enantioconvergent C(sp3)-C(sp3) bond formation reactions have been made in recent years through the use of transition-metal-catalyzed cross-coupling reactions of racemic secondary alkyl electrophiles with organometallic reagents. Herein, we report a general process for the asymmetric construction of alkyl-alkyl bonds adjacent to heteroatoms, namely, a nickel-catalyzed enantioconvergent reductive hydroalkylation of olefins with α-heteroatom phosphorus or sulfur alkyl electrophiles. Including the use of readily available olefins, this reaction has considerable advantages, such as mild reaction conditions, a broad substrate scope, and good functional group compatibility, making it a desirable alternative to traditional electrophile-nucleophile cross-coupling reactions.

Nickel-Catalyzed Enantioconvergent Reductive Hydroalkylation of Olefins with α-Heteroatom Phosphorus or Sulfur Alkyl Electrophiles.

The first electrochemical approach for nickel-catalyzed cross-electrophile coupling was developed. This method provides a novel route to 1,1-diarylalkane derivatives from simple and readily available alkyl and aryl halides in good yields and excellent regioselectivity under mild conditions. The procedure shows good tolerance for a broad variety of functional groups and both primary and secondary alkyl halides can be used. Furthermore, the reaction was successfully scaled up to the multigram scale, thus indicating potential for industrial application. Mechanistic investigation suggested the formation of a nickel hydride in the electroreductive chain-walking arylation, which led to the development of a new nickel-catalyzed hydroarylation of styrenes to provide a series of 1,1-diaryl alkanes in good yields under mild reaction conditions.

/pdf/nickel-catalyzed-chain-walking-cross-electrophile-coupling-1c3nklz0rz.pdf

Nickel-Catalyzed Chain-Walking Cross-Electrophile Coupling of Alkyl and Aryl Halides and Olefin Hydroarylation Enabled by Electrochemical Reduction.

The use of simple and easily available feedstock to quickly and efficiently obtain compounds with complex molecular structures through the transition-metal-catalyzed construction of C(sp3)–C bonds has important significance. As traditional C(sp3)–C coupling reagents, alkylmetallic reagents often have limitations such as air and moisture sensitivity and difficulties in storage. Nickel-catalyzed reductive olefin hydrocarbonation reactions use alkenes to replace organometallic reagents, reduce the synthesis steps, improve the functional group compatibility, and expand the substrate scope. This minireview discusses important progress in the hydroalkylation and hydroarylation of electronically unbiased alkenes in recent years and describes the key mechanism and applications.

Recent advances in nickel-catalyzed reductive hydroalkylation and hydroarylation of electronically unbiased alkenes

Terminal C(sp3)H alkylation of internal alkenes via Ni/H-catalyzed isomerization

An efficient nickel-catalyzed Heck-type reaction between styrenes and fluoroalkyl iodine has been developed. This novel transformation has demonstrated a broad substrate scope, mild reaction conditions and excellent E-stereoselectivity. This efficient synthetic method has been applied to the late-stage monofluoroacetation of biologically active molecules. Mechanistic investigations indicate that a monofluoroalkyl radical is involved in the catalytic cycle.

Nickel-Catalyzed Heck-Type Monofluoroacetation of Styrenes for Facile Synthesis of Allylic Fluorides.

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Terminal C(sp3)H alkylation of internal alkenes via Ni/H-catalyzed isomerization

Nickel-Catalyzed Heck-Type Monofluoroacetation of Styrenes for Facile Synthesis of Allylic Fluorides.