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

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Dasgupta, A, Stefkova, K, Babaahmadi, R, Yates, BF ORCID: 0000-0001-9663-3301, Buurma, N, Ariafard, A ORCID: 0000-0003-2383-6380, Richards, E and Melen, RL 2021 , 'Site-selective Csp3–Csp/Csp3–Csp2 cross-coupling reactions using frustrated Lewis pairs' , Journal of the American Chemical Society, vol. 143, no. 11 , pp. 4451-4464 , doi: 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
Authors/Creators:Dasgupta, A and Stefkova, K and Babaahmadi, R and Yates, BF and Buurma, N and Ariafard, A and Richards, E and Melen, RL
Journal or Publication Title: Journal of the American Chemical Society
Publisher: Amer Chemical Soc
ISSN: 0002-7863
DOI / ID Number: 10.1021/jacs.1c01622
Copyright Information:

© 2021 The Authors. Published by American Chemical Society. Licensed under the Creative Commons Attribution 4.0 International (CC BY 4.0) license (https://creativecommons.org/licenses/by/4.0/)

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