Reactivity of P–H Group of Phosphines

Troev, K.

doi:10.1016/b978-0-12-813834-2.00002-0

Cited by 16 publications

(12 citation statements)

References 317 publications

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“…Regarding the reactivity of >P(O)H derivatives, the proton exchange between the phosphorus and the oxygen atom is a critical step [17]. The trivalent form is usually more reactive according to its enhanced nucleophilicity and the lower steric hindrance.…”

Section: Introductionmentioning

confidence: 99%

A Mechanistic Study on the Tautomerism of H-Phosphonates, H-Phosphinates and Secondary Phosphine Oxides

et al. 2019

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H-phosphonates, H-phosphinates and secondary phosphine oxides may be preligands, and are important building blocks in the synthesis of pharmaceuticals, pesticides, and P-ligands. The prototropic tautomerism influenced by substituent effects plays an important role in the reactivity of these species. The main goal of our research was to study the tautomerism of the >P(O)H reagents by means of computational investigations applying several DFT methods at different levels. We focused on the effect of implicit solvents, and on explaining the observed trends with physical chemical molecular descriptors. In addition, multiple reaction pathways incorporating three P-molecules were elucidated for the mechanism of the interconversion.

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Section: Introductionmentioning

confidence: 99%

A Mechanistic Study on the Tautomerism of H-Phosphonates, H-Phosphinates and Secondary Phosphine Oxides

et al. 2019

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“…Organophosphines have found extensive use in the areas of materials science, biology, agriculture, electronics, and especially, catalysis [1][2][3][4][5][6][7]. Despite their utility, responsible use of phosphorus is imperative as a result of dwindling supply [2,3,8].…”

Section: Introductionmentioning

confidence: 99%

“…Selective carbon-phosphorus bond formation has been an on-going focus of research for these reasons [4,[9][10][11][12][13][14]. A wide range of phosphine chemistry has been developed, with metal catalyzed hydrophosphination being one of the most economic avenues for P-C bond formation.…”

Section: Introductionmentioning

confidence: 99%

Effect of Photolysis on Zirconium Amino Phenoxides for the Hydrophosphination of Alkenes: Improving Catalysis

Novas

Morris

Liptak

et al. 2021

Preprint

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A comparative study of amino phenoxide zirconium catalysts in the hydrophosphination of alkenes with diphenylphosphine reveals enhanced activity upon irradiation. The origin of improved reactivity is hypothesized to result from substrate insertion upon an n to d charge transfer of a Zr–P bond in the excited state of putative phosphido (Zr–PR2) intermediates. TD-DFT analysis reveals the lowest lying excited state in the proposed active catalysts are dominated by a P 3p to Zr 4d MLCT, presumably leading to enhanced catalysis. This hypothesis follows from triamidoamine-supported zirconium catalysts but demonstrates the generality of photocatalytic hydrophosphination with d0 metals.

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“…This process proceeds under mild conditions and occurs with alkenylazaarenes that have not previously been reported to undergo hydrophosphinylations, including β,β′-disubstituted alkenes and dienes. Our mechanistic data points to the conjugate attack of a P(III) nucleophile (generated from the tautomerization of phosphine oxide P(V)) to an alkene (activated by the coordination to a boron catalyst) for the construction of a C–P bond.…”

Section: Introductionmentioning

confidence: 99%

Boron Lewis Acid-Catalyzed Hydrophosphinylation of N-Heteroaryl-Substituted Alkenes with Secondary Phosphine Oxides

et al. 2020

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We report the boron-catalyzed hydrophosphinylation of N-heteroaryl-substituted alkenes with secondary phosphine oxides that furnishes various phosphorus-containing N-heterocycles. This process proceeds under mild conditions and enables the introduction of a phosphorus atom into multisubstituted alkenylazaarenes. The available mechanistic data can be explained by a reaction pathway wherein the C–P bond is created by the reaction between the activated alkene (by coordination to a boron catalyst) and the phosphorus(III) nucleophile (in tautomeric equilibrium with phosphine oxide).

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Reactivity of P–H Group of Phosphines

Cited by 16 publications

References 317 publications

A Mechanistic Study on the Tautomerism of H-Phosphonates, H-Phosphinates and Secondary Phosphine Oxides

A Mechanistic Study on the Tautomerism of H-Phosphonates, H-Phosphinates and Secondary Phosphine Oxides

Effect of Photolysis on Zirconium Amino Phenoxides for the Hydrophosphination of Alkenes: Improving Catalysis

Boron Lewis Acid-Catalyzed Hydrophosphinylation of N-Heteroaryl-Substituted Alkenes with Secondary Phosphine Oxides

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