4653-63-8Relevant academic research and scientific papers
Reversible Oxidation of Phosphylthionates and Phosphylselenonates with Trifluoroacetic Anhydride
Bruzik, Karol S.,Stec, Wojciech J.
, p. 6131 - 6135 (1990)
Trifluoroacetic anhydride oxidizes a variety of phosphylthionates and -selenonates into corresponding oxo products at room temperature.In the case of phosphine sulfide 1, the reaction proceeds with complete racemization, while phosphine selenide 2 is oxidized with a net inversion and a high degree of racemization.The extent of epimerization during the oxidation of diastereomeric phosphoroselenonates is much lower.The variable-temperature 31P NMR spectra show the existence of two intermediates: a phosphonium salt 12 and the pentacoordinated compound 13, both originating from the acylation of the product at phosphoryl oxygen.Two analogous intermediates containing sulfur or selenium, occuring earlier on the reaction pathway, are also postulated.The entire process is fully reversible as evidenced by the conversion of ethylmethylphenylphosphine oxide into the corresponding sulfide during the desulfurization of methyl-n-propylphenylphosphine sulfide.The equilibrium is gradually shifted into the oxidized product by the decomposition processes of trifluorothio- or trifluoroselenoacetic anhydride.
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
, (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.
The influence of radical stability of organomagnesium halide reagents on the direction of addition to an α,β-unsaturated phosphoryl group
Gatrone,Jonson
, p. 2743 - 2751 (2007/10/02)
The addition of Grignard reagents with increasing radical character to α,β-unsaturated phosphoryl groups was found to occur with a corresponding increase in the yield of the aromatic substitution products. Molecular modelling was used to determine that the radical character has a greater role in determining the degree of aromatic substitution than does steric parameters.
A new, stereoselective interconversion of phosphinothio-phosphinoseleno compounds, reduction of phosphinoseleno derivatives and retro pishchimuka rearrangement based on methylthio- and methylselenophosphonium salts chemistry
Omelanczuk, Jan
, p. 8887 - 8898 (2007/10/02)
The interconversion of thiono- into seleno compounds was found to proceed with retention of the configuration at phosphorus and the mechanistic course of this process has been proposed. The isomerization reaction of phosphinothiolates into thiono-isomers via the phosphonium salts has been developed and considered as the "retro Pishchimuka" rearrangement.
Asymmetric Synthesis of Phosphine Oxides with the Arbuzov Reaction
Kato, Takayuki,Kobayashi, Kimiko,Masuda, Shinji,Segi, Masahito,Nakajima, Tadashi,Suga, Sohei
, p. 1915 - 1918 (2007/10/02)
The Arbuzov reaction of (5S,6S)-dimethoxy-2-phenyl-1,3,2-dioxaphosphacycloheptane with various alkyl halides produced acyclic phosphinates in a moderate to high diastereomer excess.The same reaction of (1S,7S)-9,9-dimethyl-4-phenyl-3,5,8,10,4-tetraoxaphosphabicyclodecane with the alkyl halides needed the more vigorous reaction conditions and gave phosphinates in a low diastereomer excess.These phosphinates were converted into optically active phosphine oxides.
PHOSPHORORGANISCHE VERBINDUNGEN 103. Die ozonolytische Desulfurierung von Thiophosphorylverbindungen: P=S -> P=O
Horner, L.,Flemming, H. W.
, p. 245 - 252 (2007/10/02)
The sulfur atom in thiophosphorylgroups P=S is exchanged by oxygen with retention of configuration according to (1) and (2) as a result of an interaction of the P=S groups with ozone (Table 1 and 2).In dithiophosphinicacidesters only the thionosulfur is easily replaced by oxygen using ozone.The absolute configuration of the enantiomeric methyl-phenyl-phosphinicacid-p-nitrophenylesters 7 an 8 is controlled on the basis of the reaction circle (4).Serine enzymes are blocked by the phosphinicacidesters 7 and 8 by a rate factor of about 60 faster than by the corresponding thionophosphinicacidesters 5 and 6.The phosphinicacidesters 7 (and 8) have a high O-selectivity in competing reactions (7:n-BuOH:n-BuNH2 = 1:1:1) in contrast to the thionophosphinicacidesters 5 (and 6) with no selectivity (ester:amide = 4:6).
Mechanisms in Electrophilic Reactions of Reactive Nitrogen Compounds with Phosphanes
Heesing, Albert,Steinkamp, Heinz
, p. 2854 - 2864 (2007/10/02)
Chiral phosphanes were used as nucleophiles in reactions with reactive nitrogen compounds to investigate the mechanisms by stereochemical means:a) Retention on phosphorus occurs in the amination with O-(mesitylsulfonyl)hydroxylamine consistent with a Ssu
