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

Citation

Dasgupta, A and Stefkova, K and Babaahmadi, R and Yates, BF and Buurma, N and Ariafard, A and Richards, E and Melen, RL, Site-selective Csp3-Csp/Csp3-Csp2 cross-coupling reactions using frustrated Lewis pairs, Journal of the American Chemical Society, 143, (11) pp. 4451-4464. ISSN 0002-7863 (2021) [Refereed Article]


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© 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/)

DOI: doi:10.1021/jacs.1c01622

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 Details

Item Type:Refereed Article
Research Division:Chemical Sciences
Research Group:Inorganic chemistry
Research Field:Inorganic chemistry not elsewhere classified
Objective Division:Expanding Knowledge
Objective Group:Expanding knowledge
Objective Field:Expanding knowledge in the chemical sciences
UTAS Author:Babaahmadi, R (Mr Rasool Babaahmadi)
UTAS Author:Yates, BF (Professor Brian Yates)
UTAS Author:Ariafard, A (Associate Professor Alireza Ariafard)
ID Code:144118
Year Published:2021
Funding Support:Australian Research Council (DP180100904)
Web of Science® Times Cited:6
Deposited By:Chemistry
Deposited On:2021-04-21
Last Modified:2021-06-02
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