[2 + 2] Cycloaddition of phosphaalkenes as a key step for the reductive coupling of diaryl ketones to tetraaryl olefins

Arkhypchuk, Anna I.; D'Imperio, Nicolas; Wells, J.A.; Ott, Sascha

doi:10.1039/d2sc03073j

Chem. Sci.

2022

DOI: 10.1039/d2sc03073j

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[2 + 2] Cycloaddition of phosphaalkenes as a key step for the reductive coupling of diaryl ketones to tetraaryl olefins

Anna I. Arkhypchuk

Nicolas D'Imperio

J.A. Wells

et al.

Abstract: Procedures for the reductive coupling of carbonyl compounds to alkenes in the literature rely either on a radical coupling strategy, as in the McMurry coupling, or ionic pathways, sometimes catalyzed...

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Cited by 8 publications

References 39 publications

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Non‐Ionic Peterson‐Type Olefination Reactivity and its Use in a Silicon‐Promoted Carbonyl‐Carbonyl Cross Coupling Reaction

Tran,

Arkhypchuk,

Ott

2024

Angewandte Chemie

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The [2+2] cycloaddition reaction between the Si=C double bond of adamantylsilene and the carbonyl group of aliphatic, aromatic or acetylenic ketones and aldehydes is demonstrated. The product of this reaction that is central to a non‐ionic version of the Peterson olefination is an unusual four‐membered 1,2‐silaoxetane heterocycle that was characterized spectroscopically and crystallographically. In the presence of SiO2, the silaoxetane undergoes retro‐cycloaddition with the formation of alkene products. As the [2+2] cycloaddition proceeds without the necessity of any base, enolizable ketones can be converted into olefins. In addition, it is shown that the adamantylsilene can be produced in situ by a sila‐Peterson reaction, providing valuable input for the development of a new one‐pot silicon‐based reductive carbonyl‐carbonyl cross coupling methodology.

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Non‐Ionic Peterson‐Type Olefination Reactivity and its Use in a Silicon‐Promoted Carbonyl‐Carbonyl Cross Coupling Reaction

Tran,

Arkhypchuk,

Ott

2024

Angewandte Chemie

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Non‐Ionic Peterson‐Type Olefination Reactivity and its Use in a Silicon‐Promoted Carbonyl‐Carbonyl Cross Coupling Reaction

Tran,

Arkhypchuk,

Ott

2024

Angew Chem Int Ed

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Probing Radical Addition to 1‐Phosphabutadienes by Employing Muonium as a “Light Isotope” of Hydrogen

Walsgrove,

Percival,

Gates

2023

Chemistry A European J

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Understanding free radical addition to multiple bonds is important to elucidating the mechanistic details of addition polymerization reactions, albeit the fleeting radical intermediates are very difficult to detect by conventional methodologies. Muon spin spectroscopy (μSR) is a highly sensitive method that can detect radical species at 106 spins (cf. EPR: 1012 spins, NMR: 1018 spins). Herein, we employ μSR to detect the radical‐addition products from three 1‐phosphabutadiene monomers, P‐analogues of isoprene. We show that muonium (Mu), a “light” H‐atom surrogate, adds predominantly at the C4 position of the P1=C2−C3=C4 moiety to give unprecedented 1‐phosphaallyl radicals as the major products. Our structural assignments are supported by assignment of muon, phosphorus and proton hyperfine coupling constants using DFT‐calculations. A minor radical product is also detected that is tentatively assigned to an PC3‐heterocyclic free radical. On the basis of DFT‐predictions, we speculate that its formation may involve initial addition of Mu+ at the C3 position followed by electron capture. These studies provide rare insights into the prospective radical (or cationic) polymerization of 1‐phosphabutadienes, which have previously been polymerized using anionic initiation.

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[2 + 2] Cycloaddition of phosphaalkenes as a key step for the reductive coupling of diaryl ketones to tetraaryl olefins

Abstract: Procedures for the reductive coupling of carbonyl compounds to alkenes in the literature rely either on a radical coupling strategy, as in the McMurry coupling, or ionic pathways, sometimes catalyzed...

Cited by 8 publications

References 39 publications

Non‐Ionic Peterson‐Type Olefination Reactivity and its Use in a Silicon‐Promoted Carbonyl‐Carbonyl Cross Coupling Reaction

Non‐Ionic Peterson‐Type Olefination Reactivity and its Use in a Silicon‐Promoted Carbonyl‐Carbonyl Cross Coupling Reaction

Non‐Ionic Peterson‐Type Olefination Reactivity and its Use in a Silicon‐Promoted Carbonyl‐Carbonyl Cross Coupling Reaction

Probing Radical Addition to 1‐Phosphabutadienes by Employing Muonium as a “Light Isotope” of Hydrogen

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