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Radical Reactivity of Frustrated Lewis Pairs with Diaryl Esters

Soltani, Y; Dasgupta, A; Gazis, TA; Ould, DMC; Richards, E; Slater, B; Stefkova, K; ... Melen, RL; + view all (2020) Radical Reactivity of Frustrated Lewis Pairs with Diaryl Esters. Cell Reports Physical Science , 1 (2) , Article 100016. 10.1016/j.xcrp.2020.100016. Green open access

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Abstract

Advances in the chemistry of metal-free systems known as frustrated Lewis pairs (FLPs) has exposed new reactivity of the p-block elements, particularly in small-molecule activation and catalysis. Typically, the mode of activation by FLPs has been predicated on a heterolytic two-electron process, although recently, select FLPs have been shown to participate in single-electron processes. Here, we report the reaction of diaryl substituted esters with FLPs. This results in divergent pathways, one whereby the diaryl moiety is stabilized by the Lewis basic phosphine, and the alternative pathway, wherein a single-electron transfer process occurs, generating the [Mes_{3}P]+⋅/[C(H)Ar_{2}]⋅ radical ion pair. The latter species undergoes a homocoupling reaction to yield tetraphenylethane derivatives. In the presence of olefins, this reactivity can be harnessed through an sp^{2}-sp^{3} C–C heterocoupling reaction to generate α,β-substituted olefins. Notably, this work showcases an FLP approach to metal-free radical C–H bond activation with subsequent C–C bond formation, which also displays complementary reactivity to other approaches.

Type: Article
Title: Radical Reactivity of Frustrated Lewis Pairs with Diaryl Esters
Open access status: An open access version is available from UCL Discovery
DOI: 10.1016/j.xcrp.2020.100016
Publisher version: https://doi.org/10.1016/j.xcrp.2020.100016
Language: English
Additional information: © 2020 The Authors. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/).
Keywords: frustrated Lewis pair, radical, boron, phosphorus, substituted olefins, electron paramagnetic resonance spectroscopy
UCL classification: UCL
UCL > Provost and Vice Provost Offices > UCL BEAMS
UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences
UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences > Dept of Chemistry
URI: https://discovery.ucl.ac.uk/id/eprint/10125860
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