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. 2020 Aug 7;10(15):8542-8556.
doi: 10.1021/acscatal.0c02115. Epub 2020 Jul 2.

Nickel-Catalyzed Dicarbofunctionalization of Alkenes

Xiaoxu Qi  1 , Tianning Diao  1
Affiliations

Nickel-Catalyzed Dicarbofunctionalization of Alkenes

Xiaoxu Qi et al. ACS Catal. .

Abstract

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.

Keywords: alkenes; dicarbofunctionalization; nickel catalysis; selectivity.

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Conflict of interest statement

The authors declare no competing financial interest.

Figures

Figure 1.
Figure 1.
Representative pathways for nickel-catalyzed alkene difunctionalization.
Scheme 1.
Scheme 1.
Carbofunctionalization Reactions of Alkenes
Scheme 2.
Scheme 2.
Overview of Nickel-Catalyzed 1,2-Dicarbofunctionalization and Mechanistic Considerations
Scheme 3.
Scheme 3.
Two-Component Coupling of Olefin-Tethered Alkyl Halides with Zinc Reagents
Scheme 4.
Scheme 4.
Two-Component Coupling of Olefin-Tethered Aryl Halides with Boronic Acids
Scheme 5.
Scheme 5.
Two-Component Coupling of Allylarene-Tethered Esters and Amides with Boronic Acids
Scheme 6.
Scheme 6.
Two-Component Coupling of Olefin-Tethered Ketones via Enolate Addition to the Alkene
Scheme 7.
Scheme 7.
Enantioselective Intramolecular Arylalkylation
Scheme 8.
Scheme 8.
Enantioselective Keto-Acylation via Photoredox-Ni Dual Catalysis
Scheme 9.
Scheme 9.
Enantioselective Intramolecular Dicarbofunctionalization of Vinyl Boronic Esters
Scheme 10.
Scheme 10.
Regioselective 1,2-Arylalkylation of Alkenes Directed by 8-Aminoquinoline (AQ)
Scheme 11.
Scheme 11.
Regioselective Alkylarylation of Vinylarenes
Scheme 12.
Scheme 12.
Regioselective Alkylarylation of Vinyl Boronic Esters
Scheme 13.
Scheme 13.
Asymmetric 1,2-Dicarbofunctionalization of Vinylboranes
Scheme 14.
Scheme 14.
Two-Component Reductive Dicarbofunctionalization
Scheme 15.
Scheme 15.
Mechanism of Two-Component Reductive Dicarbofunctionalization of Alkenes
Scheme 16.
Scheme 16.
Proposed Mechanism of Intramolecular Enantioselective Diarylation of Enamides
Scheme 17.
Scheme 17.
Enantioselective Reductive Carboacylation of Alkenes
Scheme 18.
Scheme 18.
Intermolecular Reductive Alkylarylation of Alkenes and the Mechanistic Proposal
Scheme 19.
Scheme 19.
Intermolecular Reductive Dicarbofunctionalization by Using Directing Group
Scheme 20.
Scheme 20.
Asymmetric Reductive Diarylation of Vinylarenes
Scheme 21.
Scheme 21.
Asymmetric Reductive 1,2-Fluoroalkylarylation of Allyl Esters
Scheme 22.
Scheme 22.
Asymmetric Reductive Dicarbofunctionalization of Alkenes
See this image and copyright information in PMC

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