Nickel Complexes in C‒P Bond Formation.

Almaz A Zagidullin,Vasili A Miluykov,Il’Yas F Sakhapov,Dmitry G Yakhvarov

doi:10.3390/molecules26175283

Almaz A Zagidullin, Vasili A Miluykov + Show 2 more

Open Access

https://doi.org/10.3390/molecules26175283

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Abstract

This review is a comprehensive account of reactions with the participation of nickel complexes that result in the formation of carbon–phosphorus (C‒P) bonds. The catalytic and non-catalytic reactions with the participation of nickel complexes as the catalysts and the reagents are described. The various classes of starting compounds and the products formed are discussed individually. The several putative mechanisms of the nickel catalysed reactions are also included, thereby providing insights into both the synthetic and the mechanistic aspects of this phosphorus chemistry.

Highlights

Taking into account the use of organophosphorus compounds in organic synthesis and homogeneous catalysis, materials chemistry, agrochemical crop protection and pharmaceutical discovery, new methods for their synthesis hold particular significance [1,2,3,4,5]
This review is a comprehensive account of reactions with the participation of nickel complexes that result in the formation of carbon–phosphorus (C-P) bonds
Among the wide range of transition metals used for C−P bond construction, our attention has focused on nickel complexes

Summary

Introduction

Taking into account the use of organophosphorus compounds in organic synthesis and homogeneous catalysis, materials chemistry, agrochemical crop protection and pharmaceutical discovery, new methods for their synthesis hold particular significance [1,2,3,4,5]. An interesting version of cross-coupling with diphenylphosphane chloride catalyzed by NiCl2(dppe) (dppe—1,2-bis(diphenylphosphano)ethane) in the presence of stoichiometric amounts of metallic Zn was reported in [15] (Figure 1) In this reaction, zinc performs two functions: it reduces Ni(II) to Ni(0) and gives rise to zinc phosphide Ph2PZnCl, which reacts with ArylX. The Charettea group reported a general and efficient Ni-catalyzed cross-coupling reaction between aryl halides (iodides, bromides, chlorides) or triflates and PPh3 generating tetraarylphosphonium salts in good to high yields (63–99%) (Figure 18). This Ni-catalyzed C-P coupling is conducted in ethylene glycol using a readily available, cheap NiBr2 precatalyst and tolerates different functional groups such as alcohols, amides, ketones, aldehydes, phenols and amines [70]. A NiBr2-based catalyst was effective in C–P coupling reactions to yield tetraarylphosphonium polymers with degrees of polymerization up to about 30 [71]

Synthesis of Phosphane Oxides by C-P Cross-Coupling

Findings

Summary and Outlook