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Updated: Nov 12, 2025

Characterizing Lewis Pairs Using Titration Coupled with In Situ Infrared Spectroscopy
Published on: February 20, 2020
Site-Selective Csp-Csp/Csp-Csp Cross-Coupling Reactions Using Frustrated Lewis Pairs
Ayan Dasgupta1, Katarina Stefkova1, Rasool Babaahmadi2
1Cardiff Catalysis Institute, School of Chemistry, Cardiff University, Main Building, Park Place, Cardiff CF10 3AT, Cymru/Wales, United Kingdom.
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 Csp-Csp 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 Csp-Csp cross-coupled products was observed. However, when 1-ethynyl-2-vinylbenzene was employed, solvent-dependent site-selective Csp-Csp or Csp-Csp 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.
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