10359-36-1Relevant articles and documents
A simple and effective method for phosphoryl transfer using TiCl4 catalysis
Jones, Simon,Selitsianos, Dimitrios
, p. 3671 - 3673 (2002)
(graph presented) A number of Lewis acids have been evaluated as catalysts for the phosphoryl transfer, the most efficient being TiCl4. Application of this methodology to the phosphorylation of a number of representative target alcohols is presented.
Organocatalytic phosphorylation of alcohols using pyridine- N -oxide
Murray, James I.,Woscholski, Rudiger,Spivey, Alan C.
supporting information, p. 985 - 990 (2015/04/27)
Phosphorylation of alcohols by phosphoryl chlorides catalysed by pyridine-N-oxide is reported. The utility of this method is demonstrated through phosphorylation of primary, secondary and a tertiary alcohol as well as phenols under mild reaction conditions and with low catalyst loading (5 mol%).
Enhanced catalytic decomposition of a phosphate triester by modularly accessible bimetallic porphyrin dyads and dimers
Totten, Ryan K.,Ryan, Patrick,Kang, Byungman,Lee, Suk Joong,Broadbelt, Linda J.,Snurr, Randall Q.,Hupp, Joseph T.,Nguyen, Sonbinh T.
supporting information; experimental part, p. 4178 - 4180 (2012/05/05)
A series of metalloporphyrin dimers were modularly prepared and shown to catalyze the methanolysis of a phosphate triester, yielding rates that are large compared to the rate of the uncatalyzed reaction. Up to 1300-fold rate acceleration can be achieved v
Activating water: Important effects of non-leaving groups on the hydrolysis of phosphate triesters
Kirby, Anthony J.,Medeiros, Michelle,Oliveira, Pedro S. M.,Orth, Elisa S.,Brandao, Tiago A. S.,Wanderlind, Eduardo H.,Amer, Almahdi,Williams, Nicholas H.,Nome, Faruk
supporting information; experimental part, p. 14996 - 15004 (2012/02/03)
The high rate of spontaneous hydrolysis of tris-2-pyridyl phosphate (TPP) is explained by the activating effects of the non-leaving ("spectator" ) groups on P-OAr cleavage, and not by intramolecular catalysis. Previous work on phosphate-transfer reactions has concentrated on the contributions to reactivity of the nucleophile and the leaving group, but our results make clear that the effects of the non-leaving groups on phosphorus can be equally significant. Rate measurements for three series of phosphate triesters showed that sensitivities to the non-leaving groups are substantial for spontaneous hydrolysis reactions, although significantly smaller for reactions with good nucleophiles. There are clear differences between triaryl and dialkyl aryl triesters in sensitivities to leaving and non-leaving groups with the more reactive triaryl systems showing lower values for both βLG and βNLG. Intramolecular catalysis of the hydrolysis of TPP by the neighbouring pyridine nitrogens is insignificant, primarily because of their low basicity.
Substitution- and elimination-free phosphorylation of functionalized alcohols catalyzed by oxidomolybdenum tetrachloride
Liu, Cheng-Yuan,Pawar, Vijay D.,Kao, Jun-Qi,Chen, Chien-Tien
experimental part, p. 188 - 194 (2010/07/03)
Among 14 oxidometallic species examined for catalytic phosphorylation of the tested alcohols, oxidomolybdenum tetrachloride (MoOCl4) was found to be the most efficient with a negligible background reaction mediated by triethylamine (Et3N). The new catalytic protocol can be applied to the chemoselective phosphorylations of primary, secondary and tertiary alcohols as well as the substitution-free phosphorylations of allylic, propargylic, and benzylic alcohols. Functionalized alcohols bearing acetonide, tetrahydropyranyl ether, tert-butyldimethylsilyl ether, or ester group are also amenable to the new catalytic protocol. The most difficult scenarios involve substitution-free phosphorylations of 1-phenylethanol and 1-(2-naphthyl)ethanol which can be effected in 95 and 90% yields, respectively. ESI-MS, IR, 1H, and 31P NMR spectroscopic analyses of the reaction progress suggest the intermediacy of an alkoxyoxidomolybdenum trichloride-triethylamine adduct such as [(RO)Mo(O)Cl3-Et3N] to be responsible for the catalytic turnover.
Hydrolysis of organophosphate esters: Phosphotriesterase activity of metallo-ss-lactamase and its functional mimics
Tamilselvi,Mugesh, Govindasamy
experimental part, p. 8878 - 8886 (2010/11/02)
The phosphotriesterase (PTE) activity of a series of binuclear and mononuclear zinc(II) complexes and metallo-β-lactamase (mβl) from Bacillus cereus was studied. The binuclear complex 1, which exhibits good mβl activity, shows poor PTE activity. In contrast, complex 2, a poor mimic of mβl, exhibits much higher activity than 1. The replacement of Cl - ligands by OH- is important for the high PTE activity of complex 2 because this complex does not show any catalytic activi-ty in methanol. The natural enzyme mssl from B. cereus is also found to be an inefficient catalyst in the hydrolysis of phosphotriesters. These observations indicate that the binding of -lactam substrates at the binuclear zinc(II) center is different from that of phosphotriesters. Furthermore, phospho diesters, the products from the hydrolysis of triesters, significantly inhibit the PTE activity of mβl and its functional mimics. Although the mononuclear complexes 3 and 4 exhibited significant mβl activity, these complexes are found to be almost inactive in the hydrolysis of phosphotriesters. These observations indicate that the elimination of phosphodiesters from the reaction site is important for the PTE activity of zinc(II) complexes.
Phosphorylation of alcohols with N-phosphoryl oxazolidinones employing copper(II) triflate catalysis
Jones, Simon,Smanmoo, Chaiwat
, p. 3271 - 3274 (2007/10/03)
(Chemical Equation Presented) Phosphoryl transfer from N-phosphoryl 5,5-diphenyl oxazolidinone is efficiently catalyzed by copper(II) triflate. The utility of this method has been demonstrated in the phosphorylation of representative primary, secondary, tertiary, phenolic, and allylic alcohols. These reaction conditions are significantly milder than employing alkoxides and allow the phosphorylation of biologically relevant molecules.
N-Phosphoryl oxazolidinones as effective phosphorylating agents
Jones, Simon,Smanmoo, Chaiwat
, p. 1585 - 1588 (2007/10/03)
A number of N-phosphoryl oxazolidinones have been prepared and evaluated, the best being 5,5-diphenyl oxazolidinones, the utility of which was demonstrated in the phosphorylation of a number of representative primary, secondary, tertiary, and phenolic alcohols.
An improved method for Lewis acid catalyzed phosphoryl transfer with Ti(t-BuO)4
Jones, Simon,Selitsianos, Dimitrios,Thompson, Kate J.,Toms, Steven M.
, p. 5211 - 5216 (2007/10/03)
Several inorganic esters have been evaluated as phosphoryl transfer catalysts. Of these, Ti(t-BuO)4 was found to be the most effective catalyst giving excellent yields of the desired phosphate esters. The loading of the catalyst could be reduced to a little as 5 mol % for a majority of substrates with no loss in the yield of product. This methodology is significantly more versatile than using TiCl4 and is suitable for the phosphorylation of more complex carbohydrates and molecules of biological interest.
Synthesis of Unsymmetrical Triaryl Phosphates under Phase-Transfer Catalysis
Genkina,Shipov,Mastryukova,Kabachnik
, p. 1742 - 1744 (2007/10/03)
A Convenient general method for preparing of unsymmetrical triaryl phosphates is elaborated. The influence of the reaction conditions on the yield and purity of the target products is revealed.
