6389-79-3Relevant academic research and scientific papers
A facile and practical preparation ofP-chiral phosphine oxides
Xu, Ronghua,Gao, Zhenhua,Yu, Yiteng,Tang, Yehua,Tian, Duanshuai,Chen, Tian,Chen, Yibing,Xu, Guangqing,Shi, Enxue,Tang, Wenjun
, p. 3335 - 3338 (2021/04/07)
A practical and cost-effective synthetic method ofP-chiral diarylalkyl, aryldialkyl, and triaryl phosphine oxides by using readily available chiral diphenyl-2-pyrrolidinemethanol as the auxiliary is developed. The long-standing racemization issue during s
Scalable Enantiomeric Separation of Dialkyl-Arylphosphine Oxides Based on Host–Guest Complexation with TADDOL-Derivatives, and their Recovery
Bagi, Péter,Fogassy, Elemér,Herbay, Réka,Holczbauer, Tamás,Keglevich, Gy?rgy,Mátrav?lgyi, Béla,Madarász, János,Székely, Gy?rgy,Varga, Bence
supporting information, (2020/03/23)
Several dialkyl-arylphosphine oxides were prepared, and the enantioseparation of the corresponding racemates was elaborated with host–guest complexation using TADDOL-derivatives. The crystallization conditions were optimized and two separate crystallization methods, one in organic solvent, and the other in water, were found to yield five examples of phosphine oxides with enantiomeric excess values higher than 94 %. A gram scale resolution was performed, and both enantiomers of the methyl-phenyl-propyl-phosphine oxide were separated with (R,R)- or (S,S)-spiro-TADDOL. The intermolecular interactions responsible for the enantiomeric recognition between the chiral host and guest molecules were investigated by single-crystal X-ray diffractional structural determinations. The similarities in the structural patterns of a few diastereomeric crystals were checked by powder X-ray diffraction, as well. Organic solvent nanofiltration (OSN) was used as a scalable technique for the decomposition of the corresponding phosphine oxide–spiro-TADDOL molecular complexes, and for the recovery of the phosphine oxide enantiomers and resolving agents.
METHOD FOR PRODUCING ORGANOPHOSPHORUS COMPOUND
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Paragraph 0051; 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.
Desymmetrization of Phosphinic Acids via Pd-Catalyzed Asymmetric Allylic Alkylation: Rapid Access to P-Chiral Phosphinates
Trost, Barry M.,Spohr, Simon M.,Rolka, Alessa B.,Kalnmals, Christopher A.
supporting information, p. 14098 - 14103 (2019/10/11)
The synthesis of P-chiral compounds is challenging, especially since useful catalytic methods for preparing such molecules are scarce. Herein we disclose a desymmetrization that employs phosphinic acids as prochiral nucleophiles in a Pd-catalyzed asymmetr
Sulfinamide Phosphinates as Chiral Catalysts for the Enantioselective Organocatalytic Reduction of Imines
Chelouan, Ahmed,Recio, Rocío,Borrego, Lorenzo G.,álvarez, Eleuterio,Khiar, Noureddine,Fernández, Inmaculada
supporting information, p. 3258 - 3261 (2016/07/14)
A new type of chiral sulfinamide phosphinate catalysts with up to three stereogenic centers, readily accessible from commercially available starting materials, is reported. The naphthyl derivative SulPhos proved to be highly efficient in the organocatalyt
Stereoselective Synthesis of P-Stereogenic N-Phosphinyl Compounds
Chelouan, Ahmed,Recio, Roco,lvarez, Eleuterio,Khiar, Noureddine,Fernndez, Inmaculada
supporting information, p. 255 - 259 (2016/02/14)
A number of P-stereogenic N-phosphinyl compounds were stereoselectively prepared in good yields by a straightforward approach, thanks to the diversified and, up until now, unexplored reactivity of (R)- and (S)-dicyclohexylidene-D-glucose methyl phenyl pho
Direct conversion of phosphonates to phosphine oxides: An improved synthetic route to phosphines including the first synthesis of methyl JohnPhos
Kendall, Alexander J.,Salazar, Chase A.,Martino, Patrick F.,Tyler, David R.
supporting information, p. 6171 - 6178 (2015/02/19)
The synthesis of tertiary phosphine oxides from phosphonates was achieved reliably and in good to excellent yields using stoichiometric amounts of alkyl or aryl Grignard reagents and sodium trifluoromethanesulfonate (NaOTf). In the absence of the NaOTf additive, covalent coordination oligomers of magnesium and phosphorus species dominate the reaction, producing very low yields of phosphine oxide, but high conversions of the phosphonate starting material. Mechanistic studies revealed that a five-coordinate phosphorus species - not a phosphinate - is the reaction intermediate. A diverse array of phosphonates was converted to phosphine oxides using a variety of Grignard reagents for direct carbon-phosphorus functionalization. This new methodology especially simplifies the synthesis of dimethylphosphino (RPMe2)-type phosphines by using air-, water-, and silica-stable intermediates. To highlight this reaction, a new Buchwald-type ligand ([1,1′-biphenyl]-2-yldimethylphosphine, or methyl JohnPhos) and a classic bidentate phosphine, bis(diphenylphosphino)propane (dppp), were synthesized in excellent yields.
Formation of unexpected heterocyclic products from pyrolysis of thiocarbonyl stabilised phosphonium ylides
Aitken, R. Alan,Barker, Graeme,Cleghorn, Lee P.,Reid, Euan J.,Roberts, Sheryl S.
, p. 1135 - 1147 (2014/01/17)
Chiral phthalimido thioxo-stabilised phosphonium ylides, prepared starting from (S)-alanine and (S)-phenylalanine, undergo intramolecular Wittig reaction upon pyrolysis leading to the previously unknown pyrrolo[2,1-a]isoindol-5-one-2- thiones, rather than
Simple unprecedented conversion of phosphine oxides and sulfides to phosphine boranes using sodium borohydride
Rajendran, Kamalraj V.,Gilheany, Declan G.
supporting information; experimental part, p. 817 - 819 (2012/02/03)
A variety of phosphine oxides and sulfides can be efficiently converted directly to the corresponding phosphine boranes using oxalyl chloride followed by sodium borohydride. Optically active P-stereogenic phosphine oxides can be converted stereospecifically to phosphine boranes with inversion of configuration by treatment with Meerwein's salt followed by sodium borohydride.
