111469-75-1Relevant academic research and scientific papers
Synthesis of H-phosphinates by the UV light - Mediated fragmentation- related phosphorylation using simple P-heterocycles
Szelke, Helga,Kovacs, Janos,Keglevich, Gyoergy
, p. 2927 - 2934 (2005)
Photolysis of aryl-substituted 2,5-dihydrophosphole oxides (5a-e and 8) in the presence of methanol afforded methyl aryl-H-phosphinates (2a-e) in good yields. In the case of 1-ethyl-, cyclohexyl-, or ethoxy-2,5-dihydrophosphole oxides, the reaction was mu
Orthosilicate-mediated esterification of monosubstituted phosphinic acids
Dumond, Yves R.,Baker, Rhonda L.,Montchamp, Jean-Luc
, p. 3341 - 3344 (2000)
(matrix presented) Monosubstituted phosphinic acids are esterified with orthosilicates in excellent yields. Phosphinylidene-containing acids react selectively under these conditions, while disubstituted phosphinic acids and phosphonic acids remain unchanged. One-pot procedures are also described for the preparation of phosphinate esters from an alcohol. This novel method provides a convenient and general alternative to more commonly employed conditions such as diazomethane or carbodiimide.
Asymmetric synthesis of stereogenic phosphorus P(V) centers using chiral nucleophilic catalysis
Brichacek, Matthew,Numan, Ahmed
, (2021/07/02)
Organophosphates have been widely used in agrochemistry, as reagents for organic synthesis, and in biochemistry. Phosphate mimics possessing four unique substituents, and thereby a chirality center, are useful in transition metal catalysis and as nucleotide therapeutics. The catalytic, stereocontrolled synthesis of phosphorus‐stereogenic centers is challenging and traditionally depends on a resolution or use of stochiometric auxiliaries. Herein, enantioenriched phosphorus centers have been synthesized using chiral nucleophilic catalysis. Racemic H‐phosphinate species were coupled with nucleophilic alcohols under halogenating conditions. Chiral phosphonate products were synthesized in acceptable yields (33–95%) and modest enantioselectivity (up to 62% ee) was observed after identification of an appropriate chiral catalyst and optimization of the solvent, base, and temperature. Nucleophilic catalysis has a tremendous potential to produce enantioenriched phosphate mimics that could be used as prodrugs or chemical biology probes.
Nickel-Catalyzed Electrosynthesis of Aryl and Vinyl Phosphinates
Daili, Farah,Ouarti, Abdelhakim,Pinaud, Marine,Kribii, Ibtihal,Sengmany, Stéphane,Le Gall, Erwan,Léonel, Eric
supporting information, p. 3452 - 3455 (2020/05/25)
A mild and useful nickel-catalyzed electrochemical phosphonylation of aryl and vinyl bromides is described. We show that alkyl H-phenylphosphinates can be coupled electrochemically with functionalized aryl and vinyl bromides using very simple conditions (Fe/Ni anode, bench-stable nickel pre-catalyst, undivided cell, galvanostatic electrolysis) to furnish the corresponding aryl and vinyl phosphinates in satisfactory to good yields. Couplings can also be applied to heteroaromatic bromides with some limitations like increased propensity to hydro-dehalogenation.
Continuous flow esterification of a H-phosphinic acid, and transesterification of H-phosphinates and H-phosphonates under microwave conditions
Henyecz, Réka,Keglevich, Gy?rgy,Kiss, Nóra Zsuzsa
, (2020/02/18)
The microwave (MW)-assisted direct esterification of phenyl-H-phosphinic acid, transesterification of the alkyl phenyl-H-phosphinates so obtained, and the similar reaction of dibenzyl phosphite (DBP) were investigated in detail, and the batch accomplishme
Water determines the products: An unexpected Br?nsted acid-catalyzed PO-R cleavage of P(iii) esters selectively producing P(O)-H and P(O)-R compounds
Li, Chunya,Wang, Qi,Zhang, Jian-Qiu,Ye, Jingjing,Xie, Ju,Xu, Qing,Han, Li-Biao
supporting information, p. 2916 - 2922 (2019/06/18)
Water is found able to determine the selectivity of Br?nsted acid-catalyzed C-O cleavage reactions of trialkyl phosphites: with water, the reaction quickly takes place at room temperature to afford quantitative yields of H-phosphonates; without water, the reaction selectively affords alkylphosphonates in high yields, providing a novel halide-free alternative to the famous Michaelis-Arbuzov reaction. This method is general as it can be readily extended to phosphonites and phosphinites and a large scale reaction with much lower loading of the catalyst, enabling a simple, efficient, and practical preparation of the corresponding organophosphorus compounds. Experimental findings in control reactions and substrate extension as well as preliminary theoretical calculation of the possible transition states all suggest that the monomolecular mechanism is preferred.
Phosphinic Acid Based Linkers: Building Blocks in Metal–Organic Framework Chemistry
Hynek, Jan,Brázda, Petr,Rohlí?ek, Jan,Londesborough, Michael G. S.,Demel, Jan
supporting information, p. 5016 - 5019 (2018/03/27)
Metal–organic frameworks (MOFs) are a chemically and topologically diverse family of materials composed of inorganic nodes and organic linkers bound together by coordination bonds. Presented here are two significant innovations in this field. The first is
Selective P?C(sp3) Bond Cleavage and Radical Alkynylation of α-Phosphorus Alcohols by Photoredox Catalysis
Jia, Kunfang,Li, Junzhao,Chen, Yiyun
supporting information, p. 3174 - 3177 (2018/02/09)
Herein the first P?C(sp3) bond cleavage and radical alkynylation of α-phosphorus alcohols to construct phosphonoalkynes is reported. The phosphorus radical is generated upon P?C bond cleavage reaction via the alkoxyl radical through photoredox catalysis with cyclic iodine(III) reagents. Various arylphosphinoyl-, alkylphosphinoyl-, phosphonate-, and phosphonic amide alcohols serve as radical phosphorus precursors to construct phosphonoalkynes for the first time.
Phosphinatophenylporphyrins tailored for high photodynamic efficacy
Hynek, Jan,Konco?ová, Martina,Zelenka, Jaroslav,K?í?ová, Ivana,Ruml, Tomá?,Kubát, Pavel,Demel, Jan,Lang, Kamil
, p. 7274 - 7281 (2018/10/24)
The development of effective photosensitizers is particularly attractive for photodynamic therapy of cancer. Three novel porphyrin photosensitizers functionalized with phosphinic groups were synthesized and their physicochemical, photophysical, and photob
New method for synthesizing substituted phosphinate
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Paragraph 0032; 0037-0038, (2017/12/27)
The invention discloses a new method for synthesizing substituted phosphinate. The method comprises the step of generating the substituted phosphinate by reducing halogenated phosphonate under the effect of a reducing agent. The optimal preparation method for the substituted phosphinate is screened through a large number of experiments according to the invention; the whole process is reasonably designed; the technological operation is simple and efficient; especially, the optimal reaction conditions are screened, including reaction solvent, reaction temperature, reaction time and optimal reaction pH value; the reaction yield is obviously increased; the yield reaches up to 85-95%; the side reaction is less; the production cost is greatly lowered; the industrial production can be realized; and the method has a wide application prospect.
