Rhodium-catalysed direct hydroarylation of alkenes and alkynes with phosphines through phosphorous-assisted C\u2212H activation

Dingyi Wang,Jiasheng Qian,Yue Zhao,Yandong Wang,Zhuangzhi Shi,Ben Dong,Jinjun Zhu

doi:10.1038/s41467-019-11420-5

Dingyi Wang, Jiasheng Qian + Show 5 more

Open Access

https://doi.org/10.1038/s41467-019-11420-5

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Journal: Nature Communications	Publication Date: Aug 6, 2019
Citations: 60	License type: open-access

Affiliation: Nanjing University

Abstract

Biarylphosphines have been widely applied as ligands in various synthetic methods, especially in transition-metal-catalysed carbon-carbon and carbon-heteroatom bond cross-coupling reactions. Based on the outstanding properties of the parent scaffolds, a general method for in situ modification of the commercial tertiary phosphine ligands to access a series of ligands is in high demand. Here we show that a rhodium-catalysed system is introduced for the hydroarylation of alkenes and alkynes with tertiary phosphines through P(III)-chelation assisted C-H activation. A series of ligand libraries containing alkyl and alkenyl substituted groups with different steric and electronic properties are obtained in high yields. Furthermore, several experimental studies are performed to uncover the key mechanistic features of the linear-selective hydroarylation of alkenes and branch-selective hydroarylation of alkynes.

Highlights

Biarylphosphines have been widely applied as ligands in various synthetic methods, especially in transition-metal-catalysed carbon-carbon and carbon-heteroatom bond cross-coupling reactions
The catalytic hydroarylation reactions have focused on the development of N directing groups with different transition metal catalysts (Fig. 1b)[25,26,27,28,29,30,31,32,33,34]
The development of the PIII-chelation-assisted C–H activation in a catalytic process prompted us to consider whether these phosphines could directly undergo hydroarylation by transition metal catalysts[52,53,54,55,56,57,58]

Summary

Introduction

Biarylphosphines have been widely applied as ligands in various synthetic methods, especially in transition-metal-catalysed carbon-carbon and carbon-heteroatom bond cross-coupling reactions. The development of the PIII-chelation-assisted C–H activation in a catalytic process prompted us to consider whether these phosphines could directly undergo hydroarylation by transition metal catalysts[52,53,54,55,56,57,58] Inspired by these previous results, we report a catalytic transformation for the regioselective hydroarylation of commercially available tertiary phosphines with alkenes and alkynes through a rhodium-catalysed, P(III)-directed C–H alkylation and alkenylation (Fig. 1e). Such routes are desirable because alkyl and alkenyl-substituted phosphine ligands[59,60,61] with different steric and electronic properties can be produced by an in situ modification strategy[62]

Methods

Results

Conclusion