82180-48-1Relevant academic research and scientific papers
METHOD FOR PRODUCING ORGANOPHOSPHORUS COMPOUND
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Paragraph 0047; 0079, (2020/05/02)
PROBLEM TO BE SOLVED: To provide a method for producing an organophosphorus compound which has excellent energy efficiency without containing a halogenated alkyl or a by-product derived from a halogenated alkyl. SOLUTION: There is provided a method for producing an organophosphorus compound by reacting a trivalent organophosphorus compound represented by the following general formula (1) in the presence of a super strong acid and/or at least one acid catalyst containing a solid superstrong acid catalyst to generate a pentavalent organophosphorus compound represented by the following general formula. (where Z1 represents OR2 or R2; Z2 represents OR3 or R3; R1, R2 and R3 represent an alkyl group, an alkenyl group or the like; when R2 and R3 are an alkyl group or the like, R2 and R3 may be bonded to each other to form a cyclic structure; and R1 may be a hydrogen atom.) SELECTED DRAWING: None COPYRIGHT: (C)2020,JPOandINPIT
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.
The Palladium Acetate-Catalyzed Microwave-Assisted Hirao Reaction without an Added Phosphorus Ligand as a “Green” Protocol: A Quantum Chemical Study on the Mechanism
Keglevich, Gy?rgy,Henyecz, Réka,Mucsi, Zoltán,Kiss, Nóra Zs.
, p. 4322 - 4331 (2017/12/26)
It was proved by our experiments that on microwave irradiation, the mono- or bidentate phosphorus ligands generally applied in the palladium(II)-catalyzed P–C coupling reaction of aryl bromides and dialkyl phosphites or secondary phosphine oxides may be substituted by the excess of the >P(O)H reagent that exists under a tautomeric equilibrium. Taking into account that the reduction of the palladium(II) salt and the ligation of the palladium(0) so formed requires 3 equivalents of the P-species for the catalyst applied in a quantity of 5–10%, all together, 15–30% of the P-reagent is necessary beyond its stoichiometric quantity. In the coupling reaction of diphenylphosphine oxide, it was possible to apply diethyl phosphite as the reducing agent and as the P-ligand. The reactivities of the diethyl phosphite and diphenylphosphine oxide reagents were compared in a competitive reaction. The mechanism and the energetics of this new variation of the Hirao reaction of bromobenzene with Y2P(O)H reagents (Y=EtO and Ph) was explored by quantum chemical calculations. The first detailed study on simple reaction models justified our assumption that, under the conditions of the reaction, the trivalent form of the >P(O)H reagent may serve as the P-ligand in the palladium(0) catalyst, and shed light on the fine mechanism of the reaction sequence. The existence of the earlier described bis(palladium complex) {[H(OPh2P)2PdOAc]2} was refuted by high level theoretical calculations. This kind of complex may be formed only with chloride anions instead of the acetate anion. The interaction of palladium acetate and Y2P(O)H may result in only the formation of the [(HO)Y2P]2Pd complex that is the active catalyst in the Hirao reaction. The new variation of the Hirao reaction is of a more general value, and represents the greenest protocol, as there is no need for the usual P-ligands. Instead, the >P(O)H reagent should be used in an excess of up to 30%. Hence, the costs and environmental burdens may be decreased. (Figure presented.).
Tailoring the specificity and reactivity of a mechanism-based inactivator of glucocerebrosidase for potential therapeutic applications
Rempel, Brian P.,Tropak, Michael B.,Mahuran, Don J.,Withers, Stephen G.
supporting information; experimental part, p. 10381 - 10383 (2011/12/04)
Chaperoning an enzyme: Fluorosugar glycosidase inactivators with tunable phosphorus-based leaving groups react quickly with the catalytic nucleophile in β glucocerebrosidase (blue circle; Bn=benzyl). In Western blot analysis, Gaucher patient cells treated with these inactivators show increased intracellular levels of mutant enzyme, presumably because of increased transit from the endoplasmic reticulum (pale blue) to the lysosome (pale pink). Copyright
An unsymmetrical approach to the synthesis of bismethylene triphosphate analogues
Taylor, Scott D.,Mirzaei, Farzad,Bearne, Stephen L.
, p. 4243 - 4246 (2007/10/03)
(Chemical Equation Presented) A protected, unsymmetrical bismethylene triphosphate analogue was prepared by sequential Michaelis-Arbuzov reactions on ethyl bis(halomethyl)phosphinates. This species was monodeprotected at one of the terminal phosphonate gr
First Use of Benzyl Phosphites in the Michaelis-Arbuzov Reaction Synthesis of Mono-, Di-, and Triphosphate Analogs
Saady, Mourad,Lebeau, Luc,Mioskowski, Charles
, p. 670 - 678 (2007/10/02)
Benzyl phosphites were used in the Michaelis-Arbuzov reaction.Special experimental conditions allowed preparation of a set of phosphonate analogs of mono-, di-, and triphosphate.Furthermore, regioselective mono-deprotection mades these molecules useful building blocks for the synthesis of analogs of polyphosphorylated compounds of biological interest (e.g. nucleotides), after removal of all phosphonate benzyl ester groups under very mild conditions and high yields.
