Site-Selective Csp3-Csp/Csp3-Csp2 Cross-Coupling Reactions Using Frustrated Lewis Pairs

Ayan Dasgupta; Katarina Stefkova; Rasool Babaahmadi; Brian F Yates; Niklaas J Buurma; Alireza Ariafard; Emma Richards; Rebecca L Melen

doi:10.1021/jacs.1c01622

Site-Selective C_sp³-C_sp/C_sp³-C_sp² Cross-Coupling Reactions Using Frustrated Lewis Pairs

J Am Chem Soc. 2021 Mar 24;143(11):4451-4464. doi: 10.1021/jacs.1c01622. Epub 2021 Mar 15.

Authors

Ayan Dasgupta¹, Katarina Stefkova¹, Rasool Babaahmadi², Brian F Yates², Niklaas J Buurma¹, Alireza Ariafard², Emma Richards¹, Rebecca L Melen¹

Affiliations

¹ Cardiff Catalysis Institute, School of Chemistry, Cardiff University, Main Building, Park Place, Cardiff CF10 3AT, Cymru/Wales, United Kingdom.
² School of Natural Sciences-Chemistry, University of Tasmania Private Bag 75, Hobart, Tasmania 7001, Australia.

Abstract

The donor-acceptor ability of frustrated Lewis pairs (FLPs) has led to widespread applications in organic synthesis. Single electron transfer from a donor Lewis base to an acceptor Lewis acid can generate a frustrated radical pair (FRP) depending on the substrate and energy required (thermal or photochemical) to promote an FLP into an FRP system. Herein, we report the C_sp³-C_sp cross-coupling reaction of aryl esters with terminal alkynes using the B(C₆F₅)₃/Mes₃P FLP. Significantly, when the 1-ethynyl-4-vinylbenzene substrate was employed, the exclusive formation of C_sp³-C_sp cross-coupled products was observed. However, when 1-ethynyl-2-vinylbenzene was employed, solvent-dependent site-selective C_sp³-C_sp or C_sp³-C_sp² cross-coupling resulted. The nature of these reaction pathways and their selectivity has been investigated by extensive electron paramagnetic resonance (EPR) studies, kinetic studies, and density functional theory (DFT) calculations both to elucidate the mechanism of these coupling reactions and to explain the solvent-dependent site selectivity.