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Radical reactivity of frustrated Lewis pairs with diaryl esters

Soltani, Yashar, Dasgupta, Ayan, Gazis, Theodore A., Ould, Darren M.C., Richards, Emma, Slater, Ben, Stefkova, Katarina, Vladimirov, Vladimir Y., Wilkins, Lewis C., Willcox, Darren and Melen, Rebecca L. 2020. Radical reactivity of frustrated Lewis pairs with diaryl esters. Cell Reports Physical Science 1 (2) 10.1016/j.xcrp.2020.100016

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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 [Mes3P]+⋅/[C(H)Ar2]⋅ 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 sp2-sp3 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.

Item Type: Article
Date Type: Publication
Status: Published
Schools: Chemistry
Cardiff Catalysis Institute (CCI)
Publisher: Elsevier
ISSN: 2666-3864
Funders: EPSRC and Leverhulme Trust
Date of First Compliant Deposit: 21 February 2020
Date of Acceptance: 10 January 2020
Last Modified: 01 Oct 2020 11:10
URI: http://orca.cf.ac.uk/id/eprint/129896

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