[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 4 publications

References 39 publications

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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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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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Cationic Phosphinidene as a Versatile P₁ Building Block: [L_C–P]⁺ Transfer from Phosphonio–Phosphanides [L_C–P–PR₃]⁺ and Subsequent L_C Replacement Reactions (L_C = N-Heterocyclic Carbene)

et al. 2023

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Cationic imidazoliumyl(phosphonio)-phosphanides [L C −P−PR 3 ] + (1a−e + , L C = 4,5-dimethyl-1,3-diisopropylimidazolium-2-yl; R = alkyl, aryl) are obtained via the nucleophilic fragmentation of tetracationic tetraphosphetane [(L C −P) 4 ][OTf] 4 (2[OTf] 4 ) with tertiary phosphanes. They act as [L C −P] + transfer reagents in phospha-Wittig-type reactions, when converted with various thiocarbonyls, giving unprecedented cationic phosphaalkenes [L C −P�CR 2 ] + (5a-f[OTf]) or phosphanides [L C −P−CR(NR 2 ′)] + (6a-d[OTf]). Theoretical calculations suggest that three-membered cyclic thiophosphiranes are crucial intermediates of this reaction. To test this hypothesis, treatment of [L C −P−PPh 3 ] + with phosphaalkenes, that are isolobal to thioketones, permits the isolation of diphosphirane salts 11a,b[OTf]. Furthermore, preliminary studies suggest that the cationic phosphaalkene [L C −P�CPh 2 ] + may be employed to access rare examples of η 2 −P�C π-complexes with Pd 0 and Pt 0 when treated with [Pd(PPh 3 ) 4 ] and [Pt(PPh 3 ) 3 ] for which analogous complexes of neutral phosphaalkenes are scarce. The versatility of [L C −P] +as a valuable P 1 building block was showcased in substitution reactions of the transferred L C -substituent using nucleophiles. This is demonstrated through the reactions of 5a[OTf] and 6c[OTf] with Grignard reagents and KNPh 2 , providing a convenient, highyielding access to MesP�CPh 2 (16) and otherwise difficult-to-synthesize 1,3-diphosphetane 17 and P-aminophosphaalkenes.

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B-substituted group 1 phosphides: synthesis and reactivity

Aman,

Dostál,

Růžička

et al. 2023

Dalton Trans.

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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 4 publications

References 39 publications

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

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

Cationic Phosphinidene as a Versatile P₁ Building Block: [L_C–P]⁺ Transfer from Phosphonio–Phosphanides [L_C–P–PR₃]⁺ and Subsequent L_C Replacement Reactions (L_C = N-Heterocyclic Carbene)

B-substituted group 1 phosphides: synthesis and reactivity

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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 4 publications

References 39 publications

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

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

Cationic Phosphinidene as a Versatile P1 Building Block: [LC–P]+ Transfer from Phosphonio–Phosphanides [LC–P–PR3]+ and Subsequent LC Replacement Reactions (LC = N-Heterocyclic Carbene)

B-substituted group 1 phosphides: synthesis and reactivity

Contact Info

Product

Resources

About

Cationic Phosphinidene as a Versatile P₁ Building Block: [L_C–P]⁺ Transfer from Phosphonio–Phosphanides [L_C–P–PR₃]⁺ and Subsequent L_C Replacement Reactions (L_C = N-Heterocyclic Carbene)