Hydrofunctionalization reactions of heterocumulenes: Formation of C–X (X = B, N, O, P, S and Si) bonds by homogeneous metal catalysts

Huke, Cameron D.; Kays, Deborah L.

doi:10.1016/bs.adomc.2021.01.003

Cited by 9 publications

(8 citation statements)

References 159 publications

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“…First described in 1990, , metal-catalyzed hydrophosphination has emerged as the preeminent method to provide selectivity to hydrophosphination. Metals from most parts of the periodic table have now been reported to mediate this reaction, and these diverse catalysts show an unsurprising dissimilitude in mechanism. ,− In comparison to the challenging formation of alkyl and alkenyl phosphines from alkenes and alkynes, the hydrophosphination of heterocumulenes has been less well studied and for many substrates proceeds under neat, catalyst - free conditions. , Nevertheless, a number of catalytic approaches have recently been reported . Despite its many attractive attributes, hydrophosphination is inherently reliant on access to molecules containing P–H bonds.…”

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confidence: 99%

A Copper(I) Platform for One-Pot P–H Bond Formation and Hydrophosphination of Heterocumulenes

et al. 2022

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The reaction of phosphorus(III) esters with pinacolborane generates phosphines via the action of an NHC-copper(I) catalyst. This gives access, within minutes, to 12 P–H bonded species, including secondary and primary phosphines as well as PH3, in excellent conversions. These phosphines can be subsequently applied in the copper(I)-catalyzed hydrophosphination of heterocumulenes in a telescoped, one-pot fashion. This approach yielded 12 phosphaureas, 3 phosphaguanidines, and 2 phosphathioureas in moderate to excellent yields without the need to handle toxic, pyrophoric, or gaseous P–H bond containing compounds. The crystal structures of two of the phosphaureas, PhP(C(O)NHPh)2 and P(C(O)NHPh)3, are presented.

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A Copper(I) Platform for One-Pot P–H Bond Formation and Hydrophosphination of Heterocumulenes

et al. 2022

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“…Classical syntheses of these compounds suffer from the use of stoichiometric additives, the need for protecting groups, and poor functional group tolerance. This has prompted research into the direct addition of P–H (hydrophosphination) or P(O)–H (hydrophosphinylation) bonds to CX (X = C, O, N, S) unsaturated bonds, which has the potential to be 100% atom-efficient …”

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confidence: 99%

Catalyst-free Hydrophosphinylation of Isocyanates and Isothiocyanates under Low-Added-Solvent Conditions

Huke

Taylor

Argent

et al. 2021

ACS Sustainable Chem. Eng.

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A catalyst-free, low-solvent method for the hydrophosphinylation of isocyanates and isothiocyanates is reported. A range of phosphorus nucleophiles including secondary phosphine oxides HP(O)R 2 (R = Ph, i Pr), phosphites HP(O)(OR) 2 (R = Me, Et), and methyl phenylphosphinate were tested. The procedure tolerated isocyanates and isothiocyanates featuring a wide range of substituents and, with use of 4 equiv of 2-methyltetrahydrofuran (2-MeTHF), solid substrates can be utilized. Twenty-five compounds were prepared with improved functional group tolerance compared to previous methods allowing access to new compounds (16 are novel). Facile scale up and simple reaction conditions make this a straightforward and practical methodology for obtaining phosphorus analogues of ureas and thioureas, which are challenging to synthesize by other methods.

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“… 4 Phosphite and related H -phosphonate esters are a family of key intermediates to organophosphorus compounds via elaboration of the P–H function into P–C bonds. 5 − 11 Recent advances in biotechnology have also cleared out a path for phosphite to act as an environmentally friendly herbicide, biostimulant, and biocide in modern agriculture owing to its minimal toxicity to humans and animals, biodegradability in soil, and inability to trigger eutrophication of natural water bodies through agricultural runoff. 12 The development of transgenic crops that metabolize phosphite rather than phosphate has allowed phosphite to serve as both a fertilizer and herbicide.…”

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“…Phosphorous acid (H 3 PO 3 ) and its conjugate base, phosphite (HPO 3 2– ), have found applications as reducing agents, as cathode materials for lithium- and sodium-ion batteries, − as well as the starting material for other commercially important reduced phosphorus compounds, such as glyphosate . Phosphite and related H -phosphonate esters are a family of key intermediates to organophosphorus compounds via elaboration of the P–H function into P–C bonds. − Recent advances in biotechnology have also cleared out a path for phosphite to act as an environmentally friendly herbicide, biostimulant, and biocide in modern agriculture owing to its minimal toxicity to humans and animals, biodegradability in soil, and inability to trigger eutrophication of natural water bodies through agricultural runoff . The development of transgenic crops that metabolize phosphite rather than phosphate has allowed phosphite to serve as both a fertilizer and herbicide. , Additionally, phosphite is thought to have been a potential major nutrient in the preoxygenated Archaen oceans, and the oxidation and condensation reactivity of inorganic phosphite likely mediated prebiotic formation of condensed phosphates. − …”

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Sustainable Production of Reduced Phosphorus Compounds: Mechanochemical Hydride Phosphorylation Using Condensed Phosphates as a Route to Phosphite

et al. 2022

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In pursuit of a more sustainable production of phosphorous acid (H 3 PO 3 ), a versatile chemical with phosphorus in the +3 oxidation state, we herein report that condensed phosphates can be employed to phosphorylate hydride reagents under solvent-free mechanochemical conditions to furnish phosphite (HPO 3 2– ). Using potassium hydride as the hydride source, sodium trimetaphosphate (Na 3 P 3 O 9 ), triphosphate (Na 5 P 3 O 10 ), pyrophosphate (Na 4 P 2 O 7 ), fluorophosphate (Na 2 PO 3 F), and polyphosphate (“(NaPO 3 ) n ”) engendered phosphite in optimized yields of 44, 58, 44, 84, and 55% based on total P content, respectively. Formation of overreduced products including hypophosphite (H 2 PO 2 – ) was identified as a competing process, and mechanistic investigations revealed that hydride attack on in-situ-generated phosphorylated phosphite species is a potent pathway for overreduction. The phosphite generated from our method was easily isolated in the form of barium phosphite, a useful intermediate for production of phosphorous acid. This method circumvents the need to pass through white phosphorus (P 4 ) as a high-energy intermediate and mitigates involvement of environmentally hazardous chemicals. A bioproduced polyphosphate was found to be a viable starting material for the production of phosphite. These results demonstrate the possibility of accessing reduced phosphorus compounds in a more sustainable manner and, more importantly, a means to close the modern phosphorus cycle.

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Hydrofunctionalization reactions of heterocumulenes: Formation of C–X (X = B, N, O, P, S and Si) bonds by homogeneous metal catalysts

Cited by 9 publications

References 159 publications

A Copper(I) Platform for One-Pot P–H Bond Formation and Hydrophosphination of Heterocumulenes

A Copper(I) Platform for One-Pot P–H Bond Formation and Hydrophosphination of Heterocumulenes

Catalyst-free Hydrophosphinylation of Isocyanates and Isothiocyanates under Low-Added-Solvent Conditions

Sustainable Production of Reduced Phosphorus Compounds: Mechanochemical Hydride Phosphorylation Using Condensed Phosphates as a Route to Phosphite

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