An alternative C-P cross-coupling route for the synthesis of novel V-shaped aryldiphosphonic acids

Stephen J I Shearan; Enrico Andreoli; Marco Taddei

doi:10.3762/bjoc.18.160

An alternative C-P cross-coupling route for the synthesis of novel V-shaped aryldiphosphonic acids

Beilstein J Org Chem. 2022 Nov 7:18:1518-1523. doi: 10.3762/bjoc.18.160. eCollection 2022.

Authors

Stephen J I Shearan¹, Enrico Andreoli¹, Marco Taddei^{1

2}

Affiliations

¹ Energy Safety Research Institute, Swansea University, Fabian Way, Crymlyn Burrows, Skewen, Swansea SA1 8EN, UK.
² Dipartimento di Chimica e Chimica Industriale, Università di Pisa, Via Giuseppe Moruzzi, 13, 56124 Pisa, Italy.

Abstract

The synthesis of phosphonate esters is a topic of interest for various fields, including the preparation of phosphonic acids to be employed as organic linkers for the construction of metal phosphonate materials. We report an alternative method that requires no solvent and involves a different order of addition of reactants to perform the transition-metal-catalyzed C-P cross-coupling reaction, often referred to as the Tavs reaction, employing NiCl₂ as a pre-catalyst in the phosphonylation of aryl bromide substrates using triisopropyl phosphite. This new method was employed in the synthesis of three novel aryl diphosphonate esters which were subsequently transformed to phosphonic acids through silylation and hydrolysis.

Keywords: arylphosphonic acids; cross-coupling reaction; phosphonate esters; transition-metal catalysis.

Grants and funding

M.T. acknowledges funding from the European Union’s Horizon 2020 research and innovation program under the Marie Skłodowska-Curie grant agreement No 663830.