New strategy for the synthesis of functionalized phosphonic acids (original) (raw)

Synthesis of phosphonates from phenylphosphonic acid and its monoesters

Synthetic Communications, 2019

Possibilities for the mono-and diesterification of phenylphosphonic acid were evaluated considering the microwave(MW)-assisted direct esterification, and the alkylating esterification. It was found that regarding the monoesterification, the reaction with 15-fold alcohol excess in the presence of [bmim][BF 4 ] additive utilizing MWs is superior than the approach by alkylation. At the same time, for the conversion of the monoester intermediate to the diester, the reaction with alkyl halides in the presence of triethylamine as the base, again under MW irradiation, was found to be the method of choice. Phosphonates with both identical and different alkoxy groups were made available.

Synthesis of bis(hydroxymethyl)phosphorylated compounds, analogs of α-aminophosphonic acids or alkylidenebisphosphonic acids

Tetrahedron, 2001

ÐThe synthesis of two new series of functional phosphines oxides is described: analogs of glyphosate [a-aminomethylbis-(hydroxymethyl)phosphine oxide] and bisphosphonic acids [bis(hydroxymethyl)phosphoryl methylphosphonic acid] substituting the phosphonic group [±P(O)(OH) 2 ] by the bis(hydroxymethyl)phosphoryl group [±P(O)(CH 2 OH) 2 ], have been synthesized in good yields, using the bis(benzyloxymethyl)chloromethyl phosphine oxide as a common precursor. The further purpose of this work is to evaluate the biological interest of the bis(hydroxymethyl)phosphoryl group in comparison to the phosphonic group present in a wide range of biological molecules.

New multifunctional phosphonic acid for metal phosphonate synthesis

Journal of Molecular Structure, 2013

h i g h l i g h t s " A new multifunctional phosphonic acid, 3-amino-5-(dihydroxyphosphoryl)benzoic acid, has been synthesized and characterized. " It crystallizes in PÀ1 space group and forms a three dimensional supramolecular structure using seven hydrogen bonds. " Molecular structure makes it potentially interesting for synthesis of open framework metal phosphonates.

Phosphonic acid: preparation and applications

Beilstein Journal of Organic Chemistry, 2017

The phosphonic acid functional group, which is characterized by a phosphorus atom bonded to three oxygen atoms (two hydroxy groups and one P=O double bond) and one carbon atom, is employed for many applications due to its structural analogy with the phosphate moiety or to its coordination or supramolecular properties. Phosphonic acids were used for their bioactive properties (drug, pro-drug), for bone targeting, for the design of supramolecular or hybrid materials, for the functionalization of surfaces, for analytical purposes, for medical imaging or as phosphoantigen. These applications are covering a large panel of research fields including chemistry, biology and physics thus making the synthesis of phosphonic acids a determinant question for numerous research projects. This review gives, first, an overview of the different fields of application of phosphonic acids that are illustrated with studies mainly selected over the last 20 years. Further, this review reports the different ...

Synthesis of Phosphonate Derivatives and Phosphonate Peptide Analogues

1996

A general method for the preparation o f a wide variety o f phosphonate derivatives, including phosphonamides, thiophospbonamides, thiophosphonates, and dithiophosphonates, from reduced phosphorus intermediates has been developed. Esters (or thioesters) o f tf-phosphinates are converted to the highly reactive phosphonochloridites by non-oxidative activation with dichlorotriphenylphosphorane. The phosphonochloridites react readily with alcohols, amines and thiols and after in situ oxidation or sulfurization, phosphonate derivatives can be isolated in moderate to very good yields (47-85%). This method was used to synthesize a thiophosphonate dipeptide, Boc-Val-i/f[P(S)(OBu)0 ]Ala-C>CH3 (15b), two thiophosphonam ide dipeptides, Boc-Val-i/4 P(S)(OrBu)NH]Gly-OCH2CH3 (1 6 b) and Fm oc-A ibi/4P(S)(OBn)NH]Gly-OCH2CH3 (20), and two phosphonate dipeptides, Fmoc-Aibi^[P(0)(0Bn)NH]Gly-0CH2CH3 (1 9 ) and Fmoc-Phe-V'tP(S)(OBn)NH]GlyOCH2CH3 (21). Compounds 15b , 16b and 20 represent the fir...

Stereochemical aspects of the asymmetric synthesis of chiral α,β-dihydroxy phosphonates. Synthesis of α,β-dihydroxy phosphonic acids

Tetrahedron: Asymmetry, 1996

Steret~ontrol in the asymmetric phosphonylation of aldehydes via organophosphorous esters has bccn obtained starting from chiral aldehydes. The nature of the O-protecting group is crucial to obtain, in terms of diastereoseleetivity and chemical yields, the best results. An ab/n/t/o molecular orbital study on 2-silyioxy propanal and MM2 studies on 2-alkoxy propanai show the existence of stable cyclic and acyclic conformers, which are presumably responsible for the high syn diastereoseleetivity observed in the addition of non-metal carrying phosphites.