Α-aminophosphonate Derivatives Research Articles

Stereoselective Synthesis of α‐Amino(phenyl)methyl(phenyl)phosphinic Acids with O‐Pivaloylated D‐Galactosylamine as Chiral Auxiliary

The diastereospecific formation of β-N-glycoside-linked α-amino phosphonic acid derivatives has been achieved in high yield by a Mannich-type reaction. The reaction was performed by using O-pivaloylated galactosylamine as a chiral template and SnCl4 as a promoter in THF (see scheme).

Alum Catalyzed Convenient Synthesis of Quino[2,3-b][1,5 benzoxazepine α-Aminophosphonate Derivatives

We have described an efficient synthesis of quino[2,3-b][1,5]benzoxazepine α-aminophosphonate derivatives by the nucleophilic addition of triethyl phosphite to substituted quino[2,3-b][1,5]benzoxazepines promoted by easily available, inexpensive and mild catalyst KAl(S<TEX>$O_4)_2{\cdot}12H_2$</TEX>O(alum). The reactions proceed smoothly at room temperature under solvent-free reaction conditions and providing high yield of product in very short reaction time.

Diastereoselective Synthesis of Enantiopure α-Aminophosphonic Acid Derivatives: Pudovik Reaction in Stereoselective Synthesis (Dedicated to A. N. Pudovik, 1916–2006)

In this report, we present the application of Pudovik reaction in the synthesis of chiral organophosphorus compounds and shown this reaction to be a promising way to enantiopure aminophosphonic acid derivatives. Cyclization reactions are a new, most efficient strategy for stereoselective synthesis of α-aminophosphonates, namely an intramolecular type of interaction of the P(III) atom and an imino group.

Studies on the Contribution of Phosphoryl Group to the Non-Covalent Interaction between ATP and α-Aminophosphonic Acids Derivatives by ESI-MS and Molecular Modeling

In this work, Diisopropyl [phenyl(pyridine-4-carboxamido)methyl]phosphonate was synthesized for investigating the interaction with ATP. The noncovalent complex was observed by the Electrospray ionization Mass Spectrometry (ESI-MS). Through Molecular modeling, it was found that the non-covalent complex was stabilized by two intermolecular hydrogen bonds, which has the binding energy of -8.999 kcals/mol. In order to investigate the function of phosphoryl group in the interaction, benzoyl phenylglycine isopropyl ester was also tested, but no interaction with ATP was observed by ESI-MS. These results implied that phosphoryl group was a very important functional group to provide effective interaction site between α-Aminophosphonic acids and ATP.

An easy entry to optically active α-amino phosphonic acid derivatives using phase-transfer catalysis (PTC)

The unprecedented use of phase-transfer catalysis (PTC) in an asymmetric hydrophosphonylation reaction allows the obtainment of a range of optically active alpha-amino phosphonic acid derivatives directly from alpha-amido sulfones.

Synthesis and characterization of novel bis–(α–aminophosphonates)with terminal chromone moieties

The 1,2,4,3,5-triazadiphosphinanyl derivative 5 and bis-(α-aminophosphonate) derivatives 6 and 8a,b bearing chromone moieties were synthesized by addition of diethyl phosphite to new condensation products that formed by condensation of 4-oxo-4H-chromene-3-carboxaldehyde (1) with phosphonic dihydrazide, 1,3-diaminopropane and 1,4-diaminobutane.

Synthesis of α-Phosphorylated α,β-Unsaturated Imines and Their Selective Reduction to Vinylogous and Saturated α-Aminophosphonates

An efficient synthesis of alpha,beta-unsaturated imines derived from alpha-aminophosphonates is achieved through aza-Wittig reaction of P-trimethyl phosphazenes with beta,gamma-unsaturated alpha-ketophosphonates. Selective 1,2-reduction of such 1-azadienes affords beta,gamma-unsaturated alpha-aminophosphonates, phosphorylated analogs of vinylglycines, which are hydrogenated to yield saturated alpha-aminophosphonate derivatives.

One-pot three-component synthesis of α-amino phosphonate derivatives

Abstract A new and highly flexible procedure is described for the synthesis of α-amino-, α-hydrazino-, and α-N-hydroxyamino Phosphonates by reaction between trimethylphosphite and in situ generated imines (iminium salts, oximes, hydrazones, nitrones) by using phenyltrimethylammonium chloride as catalyst (1 mol%) in reagent grade dichloromethane at 40 °C.

Synthesis and Antiviral Bioactivities of α-Aminophosphonates Containing Alkoxyethyl Moieties

A simple, efficient, and general method has been developed for the synthesis of various alpha-aminophosphonate derivatives 4a-4l by treatment of substituted benzaldehydes and aniline with bis(2-methoxyethyl)- or bis(2-ethoxyethyl) phosphite under microwave irradiation without solvents and catalysts. The products were characterized by elemental analysis, IR, 1H-NMR, 13C- and 31P-NMR spectra. The X-ray crystallographic data of the representative compound 4l was determined. The new alpha-aminophosphonate derivatives were found to possess moderate to good antiviral activity.

Amino acids in a three-component synthesis of α-aminophosphonates derivatives

Amino acids in a three-component synthesis of α-aminophosphonates derivatives

Direct Access to Enantiomerically Enriched α-Amino Phosphonic Acid Derivatives by Organocatalytic Asymmetric Hydrophosphonylation of Imines

A simple and efficient organocatalytic enantioselective hydrophosphonylation of imines to enantiomerically enriched alpha-amino phosphonates is reported. By using 10 mol % of quinine as the catalyst in the enantioselective addition of diethyl phosphite to N-Boc protected imines, alpha-amino phosphonates are obtained in moderate to good yields and with up to 94% ee.

1-Trifluoromethyl-1-diethoxyphosphoryl Carbene: A New Synthon for the Preparation of CF3-Containing α-Hydroxy and α-Amino Phosphonic Acid Derivatives

The first synthesis of diethyl 1-diazo-2,2,2-trifluoroethylphosphonate has been developed starting from readily available compounds. The synthetic utility of this compound is demonstrated via its Rh-catalyzed insertion into O-H and N-H bonds to produce CF3-substituted α-hydroxy phosphonic and α-amino phosphonic acid derivatives

An Easy Approach to Optically Active α-Amino Phosphonic Acid Derivatives by Chiral Zn(II)-Catalyzed Enantioselective Amination of Phosphonates

A catalytic direct enantioselective electrophilic amination of beta-keto phosphonates has been developed applying chiral bisoxazoline-zinc(II) complexes as the catalyst. The reaction proceeds well for both acyclic and cyclic substrates in high yields and with up to 98% ee using azodicarboxylates as the nitrogen source. The scope of the reaction is, for example, the further transformation to optically active beta-hydroxy-alpha-amino phosphonates with very high stereoselection.

Catalytic Asymmetric Synthesis of α‐Amino Phosphonates Using Enantioselective Carbon—Carbon Bond‐Forming Reactions.

AbstractFor Abstract see ChemInform Abstract in Full Text.

Catalytic asymmetric synthesis of alpha-amino phosphonates using enantioselective carbon-carbon bond-forming reactions.

We have developed highly enantioselelctive reactions of silicon enolates with N-acyl-alpha-iminophosphonates leading to optically active alpha-amino phophonates. A copper (II)-diamine complex was shown to be effective in this reaction, and high levels of yield and selectivity were achieved. It is noteworthy that this reaction opens a way to various biologically important, optically active alpha-amino phosphonate derivatives.

Synthesis of Fluorine-Containing Cyclic α-Amino Acid and α-Amino Phosphonate Derivatives by Alkene Metathesis

The electrophilic imino esters XF2CC(=NPG)CO2Me and imino phosphonates CF3CC(=NPG)P(O)(OR)2 (PG = SO2Ph, Cbz, Boc) were transformed by nucleophilic and then electrophilic additions into fluorine-containing amino esters and amino phosphonates with two pendent alkene chains (XF2C)(CH2=CH(CH2)nC(NPG)(Z)(CH2)mCH=CH2 [Z = CO2Me, P(O)(OR)2]. The ring-closing metathesis was performed on the α-amino ester dienes with Ru=CHPh(Cl)2(PCy3)2 catalyst and afforded five-, six-, and seven-membered cyclic amino esters, whereas the α-aminophosphonate dienes were transformed with RCM catalyst [Ru=C=C=CPh2(Cl)(PCy3)(p-cymene)]OTf to give six- and seven-membered cyclic α-amino-α-(trifluoromethyl)phosphonates.

Enantioselective Construction of Quaternary α-Carbon Centers on α-Amino Phosphonates via Catalytic Asymmetric Allylation

Asymmetric allylation of α-acetamido β-keto phosphonates was promoted, in the presence of potassium tert-butoxide as a base, by a palladium catalyst prepared from [Pd(π-allyl)(cod)]BF4 and (R)-BINAP and gave the corresponding α-alkyl α-amino phosphonic acid derivatives with 65−88% ee. Diastereoselective reduction of the carbonyl group in the product was accomplished by NaBH4 or Bu4NBH4. The diastereoselection in the reduction was reversed by choice of solvent.

SYNTHESIS OF BIHETEROCYCLIC α-AMINOPHOSPHONIC ACID DERIVATIVES

We report here the synthesis of biheterocyclic α-aminophosphonic acid derivatives by 1,3 dipolar cycloaddition of acetylenic compounds, prepared in the laboratory, on α-azido α-amino phosphonic esters 1 [1a].

Asymmetric Synthesis of α-Amino Phosphonic Acids Employing the Condensation of Nitrones with Phosphite Derivatives

Abstract Chiral α-amino phosphonic acid derivatives were synthesized by condensing an enantiomerically homogeneous diazasilyl phosphite with a series of prochiral nitrones. The reactions proceed under mild conditions with moderate to high enantioselectivities and good yields.

Catalytic stereoselective synthesis of α-Amino phosphonic acid derivatives by asymmetric hydrogenation

Abstract The phosphonate analogue of α-N-benzoyl protected phenylalanine methylester has been prepared by catalytic synthesis. Commonly used Rh-complexes has been applied in asymmetric hydrogenation to check their usefulness in the standard reaction.