4218-62-6Relevant articles and documents
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%).
Base-promoted O-deprotonation/alkylation reaction of P(O)-OH compounds with alkyl halides
Xiong, Biquan,Ye, Qianqian,Feng, Xiaofeng,Zhu, Longzhi,Chen, Tieqiao,Zhou, Yongbo,Au, Chak-Tong,Yin, Shuang-Feng
, p. 9057 - 9063 (2015/03/05)
A novel base-promoted O-deprotonation/alkylation reaction of P(O)-OH compounds with alkyl halides has been developed. The protocol is practical, representing a simple way to produce a broad spectrum of functionalized phosphinates, phosphonates, and phosphates from basic starting materials with good to excellent yields. A plausible mechanism was proposed for this reaction.
Reactive intermediates in the H-phosphonate synthesis of oligonucleotides
Powles, Nicholas,Atherton, John,Page, Michael I.
experimental part, p. 5940 - 5947 (2012/08/28)
The formation of H-phosphonate diesters is an important step in the synthesis of oligonucleotides. Using diphenylchlorophosphate as the activator for the coupling step is often accompanied by side reactions as a result of self 'capping' and other reactions of the reactive intermediate. In the absence of base, the activation of ethyl H-phosphonate with diphenylchlorophosphate probably occurs through the intermediate formation of bis diethyl pyro-di-H-phosphonate rather than the expected diphenyl ethyl pyro-H-phosphonate. Pyridine acts as a nucleophilic catalyst converting diphenylchlorophosphate to its pyridinium adduct. Several side and unwanted reactions are quantified so that conditions to minimise these can be identified.
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.
Efficient and convenient one-pot synthesis of phosphoramidates and phosphates
Gupta,Acharya,Dubey,Kaushik
, p. 3403 - 3407 (2008/02/13)
A simple and efficient one-pot method is described for the synthesis of phosphoramidates/phosphates in excellent yields from dialkylphosphites and trichloroisocyanuric acid in acetonitrile and subsequent treatment with dialkyl amines/alcohols. The procedure is operationally simple, has reduced reaction times, and uses a one-pot procedure. Copyright Taylor & Francis Group, LLC.
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.
Surface-mediated solid phase reactions: A simple, efficient and base-free synthesis of phosphonates and phosphates on Al2O3
Acharya, Jyotiranjan,Shakya, Purushottam D.,Pardasani, Deepak,Palit, Meehir,Dubey, Devendra K.,Gupta, Arvind K.
, p. 194 - 196 (2007/10/03)
Al2O3-supported solvent free condensation of alkylphosphonic dichlorides with alcohols at room temperature yielded phosphorus esters in excellent yields.
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.
