Over the past 40 years, transition metal catalysis has enabled bond formation between aryl and olefinic (sp(2)) carbons in a selective and predictable manner with high functional group tolerance. Couplings involving alkyl (sp(3)) carbons have proven more challenging. Here, we demonstrate that the synergistic combination of photoredox catalysis and nickel catalysis provides an alternative cross-coupling paradigm, in which simple and readily available organic molecules can be systematically used as coupling partners. By using this photoredox-metal catalysis approach, we have achieved a direct decarboxylative sp(3)-sp(2) cross-coupling of amino acids, as well as α-O- or phenyl-substituted carboxylic acids, with aryl halides. Moreover, this mode of catalysis can be applied to direct cross-coupling of C(sp³)-H in dimethylaniline with aryl halides via C-H functionalization.

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Merging photoredox with nickel catalysis: Coupling of α-carboxyl sp3-carbons with aryl halides

The chemistry of phosphorus is nowadays rivalling that of carbon in terms of complexity and diversity. This tutorial review highlights the state-of-the-art in the field of metal-mediated activation and functionalization of white phosphorus. Particular attention is given to an illustration of the coordination abilities of the intact molecule as well as the disaggregating and reaggregating metal-mediated processes resulting in different polyphosphorus ligands from P1 to P12. The metal-promoted P–C and P–H bond forming processes are also reviewed showing that an ecoefficient catalytic protocol for transforming P4 into high value organophosphorus compounds is a concrete possibility for chemical companies.
 This tutorial review deals with the activation and functionalization of white phosphorus in the coordination sphere of transition metal complexes. Particular attention is given to the coordination abilities of the intact molecule as well as to the disaggregating and reaggregating metal-mediated processes yielding various polyphosphorus ligands from P1 to P12. The metal-promoted processes for P–C and P–H bond formation are also reviewed showing that an ecoefficient catalytic protocol for transforming P4 into high value organophosphorus compounds offers good opportunities for chemical companies.

Coordination chemistry and functionalization of white phosphorus via transition metal complexes

Various triarylphosphines have been prepared by coupling diphenylphosphine with aryl iodides with catalytic amounts of CuI in the presence of either K2CO3 or Cs2CO3, in good yields. This method can tolerate a variety of functional groups and does not require the use of expensive additives, or harsh reaction conditions, and is palladium free.

Copper-catalyzed synthesis of unsymmetrical triarylphosphines

A scalable enantioselective nickel-catalyzed electrochemical reductive homocoupling of aryl bromides has been developed, affording enantioenriched axially chiral biaryls in good yield under mild conditions using electricity as a reductant in an undivided cell. Common metal reductants such as Mn or Zn powder resulted in significantly lower yields in the absence of electric current under otherwise identical conditions, underscoring the enhanced reactivity provided by the combination of transition metal catalysis and electrochemistry.

Enantioselective Ni-Catalyzed Electrochemical Synthesis of Biaryl Atropisomers

Electron transfer in organonickel complexes of α-diimines: Versatile redox catalysts for C–C or C–P coupling reactions – A review

Highly reactive σ-organonickel complexes in electrocatalytic processes

Nickel-catalysed electrochemical coupling between mono- or di-chlorophenylphosphines and aryl or heteroaryl halides

The role of Ni(0) complexes in electrochemical phosphorylation of organic halides part 1. Factors determining catalytic activity

Erratum to “Nickel-catalysed electrochemical coupling between mono- or di-chlorophenylphosphines and aryl or heteroaryl halides”: [Journal of Organometallic Chemistry 575 (1999) 63–66]

Yuri M. Kargin

Papers

Highly reactive σ-organonickel complexes in electrocatalytic processes

Nickel-catalysed electrochemical coupling between mono- or di-chlorophenylphosphines and aryl or heteroaryl halides

The role of Ni(0) complexes in electrochemical phosphorylation of organic halides part 1. Factors determining catalytic activity

Erratum to “Nickel-catalysed electrochemical coupling between mono- or di-chlorophenylphosphines and aryl or heteroaryl halides”: [Journal of Organometallic Chemistry 575 (1999) 63–66]