- Diphenyl Diselenide-Catalyzed Synthesis of Triaryl Phosphites and Triaryl Phosphates from White Phosphorus
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Industrially important triaryl phosphites, traditionally prepared from PCl3, have been synthesized by a diphenyl diselenide-catalyzed one-step procedure involving white phosphorus and phenols, which provides a halogen- and transition metal-free way to these compounds. Subsequent oxidation of triaryl phosphites produces triaryl phosphates and triaryl thiophosphates. Phosphorotrithioates are also prepared efficiently from aromatic thiols and aliphatic thiols.
- Zhang, Yue,Cai, Ziman,Chi, Yangyang,Zeng, Xiangzhe,Chen, Shuanghui,Liu, Yan,Tang, Guo,Zhao, Yufen
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supporting information
p. 5158 - 5163
(2021/07/20)
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- Flash production of organophosphorus compounds in flow
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Flow synthesis techniques have received a significant amount of attention due to their high productivity. However, when reaction condition is heterogeneous, it is usually difficult to adapt it to flow synthesis. Herein, by selecting appropriate reagents, the synthesis of phosphate esters, which is commonly heterogeneous, was made homogeneous, enabling synthesis in flow systems. In addition, reaction rate was accelerated compared to the batch system. It was demonstrated that not only can the high productivity of flow synthesis be achieved in flow, but also high productivity can be achieved by accelerating the reaction. Finally, we demonstrated the synthesis of the Akiyama-Terada catalyst, a chiral organocatalysts, in a short period.
- Nagaki, Aiichiro,Tamaki, Takashi
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supporting information
(2021/09/09)
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- A Lewis Base Nucleofugality Parameter, NFB, and Its Application in an Analysis of MIDA-Boronate Hydrolysis Kinetics
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The kinetics of quinuclidine displacement of BH3 from a wide range of Lewis base borane adducts have been measured. Parameterization of these rates has enabled the development of a nucleofugality scale (NFB), shown to quantify and predict the leaving group ability of a range of other Lewis bases. Additivity observed across a number of series R′3-nRnX (X = P, N; R′ = aryl, alkyl) has allowed the formulation of related substituent parameters (nfPB, nfAB), providing a means of calculating NFB values for a range of Lewis bases that extends far beyond those experimentally derived. The utility of the nucleofugality parameter is explored by the correlation of the substituent parameter nfPB with the hydrolyses rates of a series of alkyl and aryl MIDA boronates under neutral conditions. This has allowed the identification of MIDA boronates with heteroatoms proximal to the reacting center, showing unusual kinetic lability or stability to hydrolysis.
- García-Domínguez, Andrés,Gonzalez, Jorge A.,Leach, Andrew G.,Lloyd-Jones, Guy C.,Nichol, Gary S.,Taylor, Nicholas P.
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supporting information
(2022/01/04)
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- Synthesis of fluorescent (benzyloxycarbonylamino)(aryl)methylphosphonates
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The synthesis of a library of structurally variable aromatic esters of (benzyloxycarbonylamino)(aryl)methylphosphonic acids is described by means of the Oleksyszyn reaction. The library was enlarged by the application of a Suzuki-Miayra approach and by preparation of mixed esters.
- Vel Gorniak, Michal Gorny,Czernicka, Anna,Mlynarz, Piotr,Balcerzak, Waldemar,Kafarski, Pawel
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supporting information
p. 741 - 745
(2014/05/06)
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- Simple phosphonic inhibitors of human neutrophil elastase
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Herein, we describe the synthesis and resulting activity of a complex series of α-aminophosphonate diaryl esters as irreversible human neutrophil elastase inhibitors and their selectivity preference for human neutrophil elastase over several other serine proteases such as porcine pancreatic elastase, trypsin, and chymotrypsin. We synthesized and examined the inhibitory potency of several new simple Cbz-protected α- aminoalkylphosphonate diaryl esters that yielded several new HNE inhibitors, where one of the obtained compounds Cbz-ValP(OC6H 4-4-COOMe)2 displayed an apparent second-order inhibition value at 33,015 M-1 s-1.
- Sieńczyk, Marcin,Winiarski, ?ukasz,Kasperkiewicz, Paulina,Psurski, Mateusz,Wietrzyk, Joanna,Oleksyszyn, Józef
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supporting information; experimental part
p. 1310 - 1314
(2011/04/16)
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- Nitrile assisted, Bronsted acid catalyzed regio and stereoselective diarylphosphonylation of allyl silyl ethers
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We have discovered a mild, catalytic protocol for the regio- and stereoselective synthesis of trisubstituted allyl diarylphosphonates from the corresponding disubstituted allyl silyl ethers, circumventing the challenges related to the preparation and availability of stereodefined trisubstituted olefins. A closely related arylation reaction was also discovered during the methodology development. By simply switching the reaction medium, high phosphonylation/arylation ratios and vice versa can be achieved. This may not be a direct result of changing solvent polarity. The allyl diarylphosphonates were evaluated as carboxylesterase inhibitors, and the screening results revealed that the inhibitory efficiency is highly related to the choice of alkenes and aryl substituents. The Royal Society of Chemistry 2010.
- Ho, Chun-Yu,Chan, Chun-Wa,Wo, Siu-Kwan,Zuo, Zhong,Chan, Lai-Ying
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supporting information; experimental part
p. 3480 - 3487
(2010/08/21)
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- New aromatic monoesters of α-aminoaralkylphosphonic acids as inhibitors of aminopeptidase N/CD13
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A series of new aromatic monoesters of α-aminoaralkylphosphonic acids were synthesized by selective hydrolysis of corresponding aromatic diesters of α-aminoaralkylphosphonic acids. New potential inhibitors of aminopeptidase N/CD13, an enzyme important in tumour angiogenesis, were developed. Some derivatives of the homophenylalanine and norleucine related monoaryl phosphonates displayed higher inhibition potency than corresponding α-aminoaralkylphosphonic acids toward aminopeptidase N/CD13. The effect of one of the new inhibitors on the growth of human PANC-1 and HT-1080 cell lines was examined, either alone or in combination with TNF-α.
- Grzywa, Renata,Sokol, Anna M.,Sieńczyk, Marcin,Radziszewicz, Magdalena,Ko?cio?ek, Beata,Carty, Michael P.,Oleksyszyn, Józef
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experimental part
p. 2930 - 2936
(2010/07/04)
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- Substituent effects on 31P NMR chemical shifts and 1J P-Se of triarylselenophosphates
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The effect of electron-withdrawing (EW) and electron-releasing (ER) substituents on the 31P NMR chemical shifts and the structural parameters of a series of tris-(p-X-aryl)selenophosphates is reported in this article. Similarly to O-aryl phosphates and O-aryl thiophosphates, EW groups attached to aromatic rings induce a shielding effect on the 31P NMR signal. After a detailed experimental and theoretical analysis, we confirmed that the selenium atom is the main part responsible for the charge density transfer toward phosphorus through a back-bonding effect. The obtained 1JP-Se values for the complete series agree with this observation. Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file.
- Dominguez, Zaira,Hernandez, Javier,Silva-Gutierrez, Lorena,Salas-Reyes, Magali,Sanchez, Mario,Merino, Gabriel
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experimental part
p. 772 - 784
(2010/07/05)
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- Substituent effects on the 31P NMR chemical shifts of arylphosphorothionates
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Six tris(aryloxy)phosphorothionates substituted in the para position of the aromatic rings were synthesized and studied by 31P NMR, X-ray diffraction techniques and ab initio calculations at a RHF/6-31G** level of theory, in order to find the main structural factors associated with the δ31P in these compounds. As the electron-withdrawing (EW) ability of the substituents was increased, an 'abnormal' shielding effect on δ31P of the arylphosphorothionates was observed. The analyses of the geometrical properties obtained through both experimental and theoretical methods showed that a propeller-type conformation is preferred for the arylphosphorothionates, except in the case of the tris(O-4-methylphenyl) phosphorothionate, since one of the aromatic rings is not rotated in the same direction as the other two in the solid state. The main features associated with the δ31P NMR of compounds 1-6 were a decrease of the averaged O-P-O angle and mainly the shortening of the PS bond length, which is consistent with an increase of the thiophosphoryl bond order as δ31P values go upfield. On the other hand, comparison of the experimental and calculated bond lengths and bond angles involving α bonded atoms to phosphorus of the six compounds suggested that stereoelectronic interactions of the type nπO-σ*PS, nπO- σ*P-OAr and nπS-σ* P-OAr could be present in the arylphosphorothionates 1-6.
- Hernández, Javier,Goycoolea, Francisco M.,Zepeda-Rivera, Denisse,Juárez-Onofre, Josué,Martínez, Karla,Lizardi, Jaime,Salas-Reyes, Magali,Gordillo, Bárbara,Velázquez-Contreras, Carlos,García-Barradas, Oscar,Cruz-Sánchez, Samuel,Domínguez, Zaira
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p. 2520 - 2528
(2007/10/03)
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- Inhibition of trypsin and urokinase by Cbz-amino(4-guanidinophenyl)methanephosphonate aromatic ester derivatives: The influence of the ester group on their biological activity
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The urokinase plasminogen activator is a trypsin-like serine protease, important in tumor development. Here, we report the synthesis and biochemical evaluation of selective and potent diaryl esters of phosphonic-type inhibitors for urokinase. We have found that the substituted phenyl ester ring has a strong influence on the inhibitory activity of these compounds. This led to the most potent phosphonic inhibitor for uPA synthesized to date.
- Sieńczyk, Marcin,Oleksyszyn, Józef
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p. 2886 - 2890
(2008/09/20)
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- Selective deoxygenation of aryl selenoxides by triaryl phosphites. Evidence for a concerted transformation
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Triaryl phosphites selectively reduce aryl selenoxides to selenides. The Hammett plot of the reactions of para-phenyl substituted triaryl phosphites with diphenyl selenoxide gave ρ=+2.3, whereas with bis(p-methoxyphenyl) selenoxide, ρ=-2.1. The results are consistent with a concerted mechanism for the oxygen transfer from Se to P.
- Stratakis, Manolis,Rabalakos, Constantinos,Sofikiti, Nikoletta
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p. 349 - 351
(2007/10/03)
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- Use of ammonium aryl H-phosphonates in the preparation of nucleoside H-phosphonate building blocks
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Ammonium 4-methylphenyl H-phosphonate 4c was used in the conversion of 5'-0-(dimethoxy-trityl)-2'-deoxynucleoside derivatives 6 into the corresponding 3'-H-phosphonates 2, which were isolated in a high state of purity and in high yield.
- Ozola, Vita,Reese, Colin B.,Song, Quanlai
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p. 8621 - 8624
(2007/10/03)
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- Syntheses und NMR-Spektren phosphororganischer Antioxidantien und verwandter Verbindungen
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The syntheses of various aliphatic, aromatic, sterically hindered, and cyclic organophosphorus compounds (phosphorous acid esters, esters chlorides and ester amides, hydrogen phosphites, phosphinates and phosphates) are reported, and general procedures for preparation are given.The compounds synthesized were investigated by means of 31P-, 1H- and 13C-n.m.r. spectroscopy, and the chemical shifts measured are listed.
- Koenig, T.,Habicher, W.D.,Haehner, U.,Pionteck, J.,Rueger, C.,Schwetlick, K.
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p. 333 - 349
(2007/10/02)
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- Selective formation of ethanol from methanol, hydrogen and carbon monoxide
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A process for the selective formation of ethanol which comprises contacting methanol, hydrogen and carbon monoxide with a catalyst system comprising cobalt acetylacetonate, a tertiary organo Group V A compound of the periodic Table, a first promoter comprising an iodine compound and a second promoter comprising a ruthenium compound.
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