795-47-1Relevant articles and documents
Heterogeneous Catalytic Method for the Copper(II)-Catalysed Addition of H-Phosphinates and Secondary Phosphine Oxides to Phenylacetylene
Bagi, Péter,Hell, Zoltán,Juhász, Kinga,Varga, Bence
, (2021/06/18)
Copper(II) on 4?? molecular sieve was found to be an efficient heterogeneous catalyst in the addition of different H-phosphinates and secondary phosphine oxides to phenylacetylene. All hydrophosphinylation reactions were completely regioselective, as only β-isomers were formed, and the E-alkenylphosphinates and E-alkenylphosphine oxides were synthesized in moderate to excellent yields. The catalyst could be reused multiple times in the reaction. Graphic Abstract: [Figure not available: see fulltext.]
Knoevenagel Condensation of Phosphinoylacetic Acids with Aldehydes: An Efficient One-Pot Strategy for the Synthesis of P-Functionalized Alkenyl Compounds
Dziuba, Kamil,Frynas, S?awomir,Szwaczko, Katarzyna
, p. 2142 - 2154 (2021/01/21)
A wide range of commercially available aldehydes have been applied to Knoevenagel condensation reaction to give E -alkenylphosphine oxides and vinylphosphine oxides. The readily available phosphinoylacetic acids derived from P(O)-H compounds were used as the starting materials in the reaction, providing a highly stereoselective and efficient method for constructing α,β-unsaturated phosphine oxides. Moreover, this simple and practical procedure provides an alternative and more environmentally friendly synthesis strategy for this type of P-functionalized alkenyl compounds.
Nickel-catalyzed coupling of R2P(O)Me (R = aryl or alkoxy) with (hetero)arylmethyl alcohols
Li, Wei-Ze,Wang, Zhong-Xia
, p. 2233 - 2242 (2021/03/24)
α-Alkylation of methyldiarylphosphine oxides with (hetero)arylmethyl alcohols was performed under nickel catalysis. Various arylmethyl and heteroarylmethyl alcohols can be used in this transformation. A series of methyldiarylphosphine oxides were alkylated with 30-90% yields. Functional groups on the aromatic rings of methyldiarylphosphine oxides or arylmethyl alcohols including OMe, NMe2, SMe, CF3, Cl, and F groups can be tolerated. The conditions are also suitable for the α-alkylation reaction of dialkyl methylphosphonates.
Copper-Catalyzed Vicinal Cyano-, Thiocyano-, and Chlorophosphorylation of Alkynes: A Phosphinoyl Radical-Initiated Approach for Difunctionalized Alkenes
Li, Cheng-Kun,Li, Jian-An,Shoberu, Adedamola,Tao, Ze-Kun,Zhang, Wei,Zou, Jian-Ping
supporting information, p. 4342 - 4347 (2021/06/28)
A copper-catalyzed difunctional cyano-, thiocyano-, and chlorophosphorylation reaction of alkynes with P(O)-H compounds and coupling partners (TBACN, TMSNCS, TMSCl) is described. The reaction introduces versatile groups (-P(O)R2 and -CN, -SCN, or -Cl) to form tri- and tetrasubstituted alkenyl phosphine oxides/phosphonates regio- and stereoselectively.
Oxidative Addition of Secondary Phosphine Oxides through Rh(I) Center: Hydrido-Phosphinito-Rh(III) Complexes and their Catalytic Activity in Hydrophosphinylation of Alkynes
Almenara, Naroa,Barquin, Montserrat,Huertos, Miguel A.,Garralda, María A.
supporting information, p. 4935 - 4945 (2021/11/09)
The reaction of [Rh(μ-Cl)(cod)]2 with diimines, differing in their steric and electronic properties, and with diphenylphosphine oxide leads to the oxidative addition products, hydrido-phosphinito-Rh(III) complexes {Rh(PPh2OH)(PPh2O)(NN)(H)Cl} (1), stabilized by the formation of a hydrogen bonded phosphinous acid-phosphinito quasi-chelate [(PO???HOP)-κ2P]. Exchange of hydride by chloride to afford {Rh(PPh2OH)(PPh2O)(NN)Cl2} (2) occurs in hydrido complexes containing low steric hindrance diimines and is inhibited for complexes containing encumbered diimines. Complexes 1 react with BF3?OEt2 with exchange of the acidic proton by BF2, and transformation of the quasi-chelating PO???HOP into a chelating PO-BF2-OP ligand in {Rh{(PPh2O)2BF2}(NN)(H)Cl} (3). The reaction of [Rh(μ-Cl)(nbd)]2 or [Rh(acac)(nbd)] with diphenylphosphine oxide leads to coordinatively unsaturated nortricyclyl-phosphinito-Rh(III) complexes, {Rh(PPh2OH)(PPh2O)(ntyl)(μ-Cl)}2 (4) or {Rh(PPh2OH)(PPh2O)(ntyl)(acac)} (6), respectively. Their reaction with BF3?OEt2 results in the corresponding {Rh{(PPh2O)2BF2}(ntyl)(μ-Cl)}2 (5) or {Rh{(PPh2O)2BF2}(ntyl)(acac)} (7). Some of these new complexes have shown catalytic activity in hydrophosphinylation of alkynes, with {Rh(PPh2OH)(PPh2O)(NN)(H)Cl} containing encumbered NN being efficient and regioselective catalysts in the hydrophosphinylation of phenylacetylene with diphenylphosphine oxide to produce (E)-diphenyl(styryl)phosphine oxide.
Controllable phosphorylation of thioesters: Selective synthesis of aryl and benzyl phosphoryl compounds
Xu, Kaiqiang,Liu, Long,Li, Zhaohui,Huang, Tianzeng,Xiang, Kang,Chen, Tieqiao
, p. 14653 - 14663 (2020/12/29)
The controllable phosphorylations of thioesters were developed. When the reaction was catalyzed by a palladium catalyst, aryl or alkenyl phosphoryl compounds were generated through decarbonylative coupling, while the benzyl phosphoryl compounds were produced through deoxygenative coupling when the reaction was carried out in the presence of only a base.
Scope and Limitations of the s-Block Metal-Mediated Pudovik Reaction
Fener, Benjamin E.,Schüler, Philipp,Ueberschaar, Nico,Bellstedt, Peter,G?rls, Helmar,Krieck, Sven,Westerhausen, Matthias
supporting information, p. 7235 - 7243 (2020/05/18)
The hydrophosphorylation of phenylacetylene with di(aryl)phosphane oxides Ar2P(O)H (Pudovik reaction) yields E/Z-isomer mixtures of phenylethenyl-di(aryl)phosphane oxides (1). Alkali and alkaline-earth metal di(aryl)phosphinites have been studi
Cobaloxime Catalysis: selective synthesis of alkenylphosphine oxides under visible light
Liu, Wen-Qiang,Lei, Tao,Zhou, Shuai,Yang, Xiu-Long,Li, Jian,Chen, Bin,Sivaguru, Jayaraman,Tung, Chen-Ho,Wu, Li-Zhu
supporting information, p. 13941 - 13947 (2019/09/30)
Direct activation of H-phosphine oxide to react with an unsaturated carbon-carbon bond is a straightforward approach for accessing alkenylphosphine oxides, which shows significant applications in both synthetic and material fields. However, expensive metals and strong oxidants are typically required to realize the transformation. Here, we demonstrate the utility of earth-abundant cobaloxime to convert H-phosphine oxide into its reactive radical species under visible light irradiation. The radical species thus generated can be utilized to functionalize alkenes and alkynes without any external photosensitizer and oxidant. The coupling with terminal alkene generates E-alkenylphosphine oxide with excellent chemo- A nd stereoselectivity. The reaction with terminal alkyne yields linear E-alkenylphosphine oxide via neutral radical addition, while addition with internal ones generates cyclic benzophosphine oxides and hydrogen. Mechanistic studies on radical trapping experiments, electron spin resonance studies, and spectroscopic measurements confirm the formation of phosphinoyl radical and cobalt intermediates that are from capturing the electron and proton eliminated from H-phosphine oxide. The highlight of our mechanistic investigation is the dual role played by cobaloxime, viz., both as the visible light absorber to activate the P(O)-H bond as well as a hydrogen transfer agent to influence the reaction pathway. This synergetic feature of the cobaloxime catalyst preforming multiple functions under ambient condition provides a convergent synthetic approach to vinylphosphine oxides directly from H-phosphine oxides and alkenes (or alkynes).
Cobaloxime Catalysis: Selective Synthesis of Alkenylphosphine Oxides under Visible Light
Liu, Wen-Qiang,Lei, Tao,Zhou, Shuai,Yang, Xiu-Long,Li, Jian,Chen, Bin,Sivaguru, Jayaraman,Tung, Chen-Ho,Wu, Li-Zhu
supporting information, p. 13941 - 13947 (2019/09/30)
Direct activation of H-phosphine oxide to react with an unsaturated carbon-carbon bond is a straightforward approach for accessing alkenylphosphine oxides, which shows significant applications in both synthetic and material fields. However, expensive metals and strong oxidants are typically required to realize the transformation. Here, we demonstrate the utility of earth-abundant cobaloxime to convert H-phosphine oxide into its reactive radical species under visible light irradiation. The radical species thus generated can be utilized to functionalize alkenes and alkynes without any external photosensitizer and oxidant. The coupling with terminal alkene generates E-alkenylphosphine oxide with excellent chemo- and stereoselectivity. The reaction with terminal alkyne yields linear E-alkenylphosphine oxide via neutral radical addition, while addition with internal ones generates cyclic benzophosphine oxides and hydrogen. Mechanistic studies on radical trapping experiments, electron spin resonance studies, and spectroscopic measurements confirm the formation of phosphinoyl radical and cobalt intermediates that are from capturing the electron and proton eliminated from H-phosphine oxide. The highlight of our mechanistic investigation is the dual role played by cobaloxime, viz., both as the visible light absorber to activate the P(O)-H bond as well as a hydrogen transfer agent to influence the reaction pathway. This synergetic feature of the cobaloxime catalyst preforming multiple functions under ambient condition provides a convergent synthetic approach to vinylphosphine oxides directly from H-phosphine oxides and alkenes (or alkynes).
Practical C–P bond formation via heterogeneous photoredox and nickel synergetic catalysis
Koranteng, Ernest,Liu, Yi-Yin,Liu, Si-Yue,Wu, Qiang-Xian,Lu, Liang-Qiu,Xiao, Wen-Jing
, p. 1841 - 1846 (2019/11/11)
An efficient C–P bond formation reaction was developed by virtue of the synergetic catalysis strategy by merging heterogeneous photocatalysis and nickel catalysis. This platform utilizing cadmium sulfide semiconductors as heterogeneous photocatalysts and
