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Site-selective Csp3–Csp/Csp3–Csp2 cross-coupling reactions using frustrated Lewis pairs

Dasgupta, Ayan, Stefkova, Katarina, Babaahmadi, Rasool, Yates, Brian F., Buurma, Niklaas J., Ariafard, Alireza, Richards, Emma and Melen, Rebecca L. 2021. Site-selective Csp3–Csp/Csp3–Csp2 cross-coupling reactions using frustrated Lewis pairs. Journal of the American Chemical Society 143 (11) , pp. 4451-4464. 10.1021/jacs.1c01622

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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 Csp3–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 Csp3–Csp cross-coupled products was observed. However, when 1-ethynyl-2-vinylbenzene was employed, solvent-dependent site-selective Csp3–Csp or Csp3–Csp2 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.

Item Type: Article
Date Type: Publication
Status: Published
Schools: Chemistry
Cardiff Catalysis Institute (CCI)
Publisher: American Chemical Society
ISSN: 0002-7863
Funders: EPSRC and Leverhulme Trust
Date of First Compliant Deposit: 19 March 2021
Date of Acceptance: 2 March 2021
Last Modified: 12 May 2021 09:40
URI: http://orca.cardiff.ac.uk/id/eprint/139916

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