Metallfreie N−H‐Bindungsaktivierung mit Phospha‐Wittig Reagenzien**

Dankert, Fabian; Siewert, Jan‐Erik; Gupta, Priyanka; Weigend, Florian; Hering‐Junghans, Christian

doi:10.1002/ange.202207064

Cited by 5 publications

(1 citation statement)

References 71 publications

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“…Importantly, the first transfers of the parent phosphinidene, [H–P], were observed from II . Carbene-phosphinidene adducts III and phosphanylidenephosphoranes IV (or “phospha-Wittig reagents”) have been shown to transfer aryl- and alkyl-substituted phosphinidenes to a wide range of substrates [e.g., organic electrophiles, aldehydes, NHCs (N-heterocyclic carbenes), isonitriles, ammonia, and Al I species . Diphosphadiboretane V has been utilized as a [Mes*–P] transfer agent to ketones, amides, and esters in the unprecedented phospha-bora-Wittig reaction .…”

Section: Introductionmentioning

confidence: 99%

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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Section: Introductionmentioning

confidence: 99%

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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Frustrated Lewis Pair Adduct of Atomic P(−1) as a Source of Phosphinidenes (PR), Diphosphorus (P₂), and Indium Phosphide

et al. 2023

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We report phosphinidenes (PR) stabilized by an intramolecular frustrated Lewis pair (FLP) chelate. These adducts include the parent phosphinidene, PH, which is accessed via thermolysis of coordinated HPCO. The reported FLP‐PH species acts as a springboard to other phosphorus‐containing compounds, such as FLP‐adducts of diphosphorus (P2) and InP3. Our new adducts participate in thermal‐ or light‐induced phosphinidene elimination (of both PH and PR, R=organic group), transfer P2 units to an organic substrate, and yield the useful semiconductor InP at only 110 °C from solution.

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Aromative Dephosphinidenation of a Bisphosphirane‐Fused Anthracene toward E−H (E=H, Si, N and P) Bond Activation

Luo,

Liu,

Huang

et al. 2024

Angewandte Chemie

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A bisphosphirane‐fused anthracene (5) was prepared by treatment of a sterically encumbered amino phosphorus dichloride (3) with MgA•3THF (A = anthracene). X‐ray diffraction analysis revealed a pentacyclic framework consisting of 5 with two phosphirane rings fused to the anthracene in a trans‐fashion. Compound 5 has been shown to be an efficient phosphinidene synthon, readily liberating two transient phosphinidene units for subsequent downstream bond activation via the reductive elimination of anthracene under mild conditions. The formal oxidative addition of H2 and E‐H (E = Si, N, P) bonds by the liberated phosphinidene provided diphosphine and substituted phosphines. Furthermore, phosphinidene transfer to alkenes and alkynes smoothly yielded the corresponding phosphiranes and phosphirenes. The mechanism of the H2 activation by 5 was investigated by density functional theory (DFT) calculations.

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Metallfreie N−H‐Bindungsaktivierung mit Phospha‐Wittig Reagenzien**

Cited by 5 publications

References 71 publications

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)

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)

Frustrated Lewis Pair Adduct of Atomic P(−1) as a Source of Phosphinidenes (PR), Diphosphorus (P₂), and Indium Phosphide

Aromative Dephosphinidenation of a Bisphosphirane‐Fused Anthracene toward E−H (E=H, Si, N and P) Bond Activation

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Metallfreie N−H‐Bindungsaktivierung mit Phospha‐Wittig Reagenzien**

Cited by 5 publications

References 71 publications

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)

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)

Frustrated Lewis Pair Adduct of Atomic P(−1) as a Source of Phosphinidenes (PR), Diphosphorus (P2), and Indium Phosphide

Aromative Dephosphinidenation of a Bisphosphirane‐Fused Anthracene toward E−H (E=H, Si, N and P) Bond Activation

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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)

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)

Frustrated Lewis Pair Adduct of Atomic P(−1) as a Source of Phosphinidenes (PR), Diphosphorus (P₂), and Indium Phosphide