Cyclic organophosphorus compounds. I. Synthesis and infrared spectral studies of cyclic hydrogen phosphites and thiophosphites

Zwierzak, A.

doi:10.1139/v67-411

Cited by 126 publications

(69 citation statements)

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“…The phosphorus reagent 1 was first prepared 11 in 1967 from pinacol and phosphorus trichloride in the presence of triethylamine and purified by distillation under vacuum. Since then, this reagent has been used as a derivatizing agent in several applications related to the analysis of lignin by Argyropoulos' group, 12,13 coal materials by Verkade's group 14 and polymeric materials.…”

Section: Phosphorus Reagentmentioning

confidence: 99%

³¹P NMR spectroscopy in the quality control and authentication of extra‐virgin olive oil: A review of recent progress

Dais

Spyros

2007

Magnetic Reson in Chemistry

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This review is a brief account on the application of a novel methodology to the quality control and authentication of extra-virgin olive oil. This methodology is based on the derivatization of the labile hydrogens of functional groups, such as hydroxyl and carboxyl groups, of olive oil constituents with the phosphorus reagent 2-chloro-4,4,5,5-tetramethyldioxaphospholane, and the use of the 31 P chemical shifts to identify the phosphitylated compounds. Various experimental aspects such as pertinent instrumentation, sample preparation, acquisition parameters and properties of the phosphorus reagent are reviewed. The strategy to assign the 31 P signals of the phosphitylated model compounds and olive oil constituents by employing 1D and 2D NMR experiments is presented. Finally, the capability of this technique to assess the quality and the genuineness of extra-virgin olive oil and to detect fraud is discussed.

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Section: Phosphorus Reagentmentioning

confidence: 99%

³¹P NMR spectroscopy in the quality control and authentication of extra‐virgin olive oil: A review of recent progress

Dais

Spyros

2007

Magnetic Reson in Chemistry

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“…D-Glyceric acid was converted into its methyl ester by using diazomethane, and a mixture of the ester 1 and ethanol was allowed to react with PC13 in anhydrous benzene. After workup, the cyclic hydrogen phosphite was treated with sulfur/triethylamine (3,4) to give the pair of diastereoisomers 2. On treatment with aqueous triethylamine these compounds were converted into the diastereoisomers of the cyclic 2,3-phosphorothioate of D-glycerate (3a and 3b) in 48% yield from 1.…”

Section: Methodsmentioning

confidence: 99%

“…2 shows 3a) by Li18OH [approximately 1 M, prepared from metallic lithium and H2180 (97.3% atom excess 180)] at room temperature for 3 hr yielded a mixture of the 2-and 3-phosphorothioates of D-glycerate (4 and 5) in 75:25 ratio, as estimated by gas chromatography of the trimethylsilyl derivatives. This mixture was subjected to the following conversions (see Fig.…”

Section: Methodsmentioning

confidence: 99%

Adenosine 5'-O-([gamma-18O]gamma-thio)triphosphate chiral at the gamma-phosphorus: stereochemical consequences of reactions catalyzed by pyruvate kinase, glycerol kinase, and hexokinase.

Orr¹,

Simon²,

Jones³

et al. 1978

Proc. Natl. Acad. Sci. U.S.A.

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Our understanding of the molecular details of enzyme-catalyzed phosphoryl group transfer processes is still rudimentary, despite the importance of phosphokinases in the synthesis and utilization of ATP. The methods available for mechanistic investigation of these reactions have not provided unambiguous answers to such fundamental questions as whether covalent phosphoryl-enzymes are kinetically obligatory (1) and how the rates of phosphoryl group transfers are accelerated (2). We report here a stereochemical approach to these problems, and present evidence that three kinases [pyruvate kinase (ATP: pyruvate 2-O-phosphotransferase; EC 2.7.1.40), glycerol kinase (ATP:glycerol 3-phosphotransferase; EC 2.7.1.30), and hexokinase (ATP:hexose 6-phosphotransferase; EC 2.7.1.1)] not only catalyze the phosphoryl transfers to ADP with complete stereospecificity, but that each also follows the same stereochemical course (i.e., retention or inversion) with respect to the chirality of the phosphoryl group transferred. EXPERIMENTALThe 2-and 3-[180]phosphorothioate esters of D-glycerate, chiral at phosphorus, were prepared as shown in Figs. 1 and 2. All reactions were monitored by thin-layer chromatography, and the purified products were characterized by 31P nuclear magnetic resonance, by gas chromatography and mass spectrometry of the trimethylsilyl derivatives, and by enzymic assay where appropriate. All enzymes used were of the highest grade available from Sigma, and were dialyzed against 100 mM triethanolamine-HCl buffer, pH 7.5. D-Glyceric acid was converted into its methyl ester by using diazomethane, and a mixture of the ester 1 and ethanol was allowed to react with PC13 in anhydrous benzene. After workup, the cyclic hydrogen phosphite was treated with sulfur/triethylamine (3, 4) to give the pair of diastereoisomers 2. On treatment with aqueous triethylamine these compounds were converted into the diastereoisomers of the cyclic 2,3-phosphorothioate of D-glycerate (3a and 3b) in 48% yield from 1. (The methyl ester hydrolyzes under these mild conditions, presumably catalyzed by the neighboring phosphorothioate.) The diastereoisomers of 3a and 3b were separated by careful ion-exchange chromatography on DEAE-cellulose; each diastereoisomer was isolated in greater than 98% purity. This separation was conveniently monitored by gas chromatography of the trimethylsilyl derivatives.Hydrolytic ring opening of an isolated diastereoisomer of 3 (whether the diastereoisomer used was actually 3a or 3b is unknown, but for the purposes of illustration, Fig. 2 shows 3a) by Li18OH [approximately 1 M, prepared from metallic lithium and H2180 (97.3% atom excess 180)] at room temperature for 3 hr yielded a mixture of the 2-and 3-phosphorothioates of D-glycerate (4 and 5) in 75:25 ratio, as estimated by gas chromatography of the trimethylsilyl derivatives. This mixture was subjected to the following conversions (see Fig. 3).Route z. Treatment of the mixture (of 4 and 5) with sodium acetate buffer at pH 5.4 caused the preferential loss of sulfur ...

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“…AIBN was purified by recrystallization from diethyl ether and stored in the refrigerator. The cyclic phosphonate 9 [14] and imidazolium salt IPr·HCl [15] were prepared according to the literature.…”

Section: Experimental Section General Conditionsmentioning

confidence: 99%

Efficient and Selective Rhodium‐Catalyzed Hydrophosphorylation of Dienes

2006

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Abstract:The hydrophosphorylation of a model 1,6-diene having a terminal and an internal alkene function has been investigated. Free radical protocols lead invariably to mixtures of cyclic phosphonate products, due to rapid cyclization of the intermediary radical species. Rhodium catalysis using a cyclic pinacol-derived phosphonate provides an efficient technique for the highly selective (> 99 %) hydrophosphorylation at the terminal alkene function. In situ modification of Wilkinsons complex by addition of 2-50 equivalents (vs. Rh) of a monophosphine (PCy 3 > PPh 3 ) or carbene ligand greatly improves the catalyst performances (TON up to 2250 mol phosphonate/mol Rh). An even more efficient system was obtained with 2 equivalents (vs. Rh) of the bidentate 1,6-bis(diphenylphosphino)hexane ligand, which affords so far unprecedented high catalytic productivity (TON up to 4 550 mol phosphonate/mol Rh) and activity (TOF up to 250 h À1 ).

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Cyclic organophosphorus compounds. I. Synthesis and infrared spectral studies of cyclic hydrogen phosphites and thiophosphites

Cited by 126 publications

References 0 publications

³¹P NMR spectroscopy in the quality control and authentication of extra‐virgin olive oil: A review of recent progress

³¹P NMR spectroscopy in the quality control and authentication of extra‐virgin olive oil: A review of recent progress

Adenosine 5'-O-([gamma-18O]gamma-thio)triphosphate chiral at the gamma-phosphorus: stereochemical consequences of reactions catalyzed by pyruvate kinase, glycerol kinase, and hexokinase.

Efficient and Selective Rhodium‐Catalyzed Hydrophosphorylation of Dienes

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Cyclic organophosphorus compounds. I. Synthesis and infrared spectral studies of cyclic hydrogen phosphites and thiophosphites

Cited by 126 publications

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31P NMR spectroscopy in the quality control and authentication of extra‐virgin olive oil: A review of recent progress

31P NMR spectroscopy in the quality control and authentication of extra‐virgin olive oil: A review of recent progress

Adenosine 5'-O-([gamma-18O]gamma-thio)triphosphate chiral at the gamma-phosphorus: stereochemical consequences of reactions catalyzed by pyruvate kinase, glycerol kinase, and hexokinase.

Efficient and Selective Rhodium‐Catalyzed Hydrophosphorylation of Dienes

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³¹P NMR spectroscopy in the quality control and authentication of extra‐virgin olive oil: A review of recent progress

³¹P NMR spectroscopy in the quality control and authentication of extra‐virgin olive oil: A review of recent progress