Synthesis Of Phosphonic Acid Analogues Research Articles

Chemoenzymatic Synthesis of Phosphonic Acid Analogues of L‐Lysine, L‐Proline, L‐Ornithine, and L‐Pipecolic Acid of 99 % ee – Assignment of Absolute Configuration to (–)‐Proline

Abstract(±)‐ω‐Halo‐α‐(chloroacetoxy)phosphonates were kinetically resolved by use of a protease (Chirazyme® P‐2). The esters recovered at levels of conversion between 56 and 72 % furnished (S)‐alcohols of 99 % ee. These were converted via azides into the phosphonic acid analogues of L‐lysine, L‐proline, L‐ornithine and L‐pipecolic acid. (–)‐Phosphaproline was transformed into crystalline ureas derived from (R)‐ and (S)‐1‐phenylethyl isocyanate. X‐ray structure analyses revealed that the levorotary phosphaproline has the R configuration, contrary to earlier reports.

Phosphonoxins II: Diastereoselective Synthesis of Phosphonic Acid Analogues of Polyoxins

A diastereoselective synthesis of polyoxin analogues termed phosphonoxin B1 and B2 has been achieved. The key step was sulfinimine-mediated asymmetric formation of ( RS ,2S,3S,4S)-beta-aminophosphonate 3a or (SS ,2R,3S,4S)-beta-aminophosphonate 7 as the major diastereoisomer. A double stereodifferentiation effect was not observed, and the diastereoselectivity is controlled by the absolute configuration of the sulfinyl group.

Asymmetric synthesis of phosphonic acid analogues for acylcarnitine

Phosphonic acid analogues of acylcarnitine were prepared in an optically active form expecting CPT I inhibitory activities. The synthetic methodology was based on catalytic asymmetric dihydroxylation of β,γ-unsaturated phosphonates and subsequent regioselective amination via the cyclic sulfates.

Synthesis of Chiral γ‐Amino‐β‐hydroxyphosphonate Derivatives from Unsaturated Phosphonates.

AbstractFor Abstract see ChemInform Abstract in Full Text.

Synthesis of Chiral γ-Amino-β-hydroxyphosphonate Derivatives from Unsaturated Phosphonates

γ-Amino-β-hydroxyphosphonates, useful intermediates for the synthesis of phosphonic acid analogues of carnitine, were prepared as their protected derivatives in an enantioselective manner from β,γ-unsaturated phosphonatesthrough asymmetric dihydroxylation and subsequent regioselective amination via the cyclic sulfates.

ChemInform Abstract: Enzymes in Organic Chemistry. Part 9. Chemo‐enzymatic Synthesis of Phosphonic Acid Analogues of L‐Valine, L‐Leucine, L‐Isoleucine, L‐Methionine and L‐α‐Aminobutyric Acid of High Enantiomeric Excess.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Enzymes in organic chemistry. Part 9: Chemo-enzymatic synthesis of phosphonic acid analogues of l-valine, l-leucine, l-isoleucine, l-methionine and l-α-aminobutyric acid of high enantiomeric excess

Diisopropyl α-chloroacetoxyphosphonates derived from propanal, isobutanal, 3-methylmercaptopropanal, 3-methylbutanal and ( S)-2-methylbutanal were resolved by enzyme-catalysed hydrolysis. Lipases preferentially hydrolysed the ( S)-esters and protease Chirazyme ® P-2 the ( R)-esters. Replacing the isopropyl groups by t-butyl groups reduced the reaction rate; replacing them by a 2,2-dimethylpropane-1,3-diyl group increased the reaction rate. ( S)-α-Hydroxyphosphonates (ee 92–99%), obtained with the protease except one, were transformed into phosphonic acid analogues of l-valine, l-leucine, l-isoleucine, l-methionine and l-α-aminobutyric acid. Their enantiomeric purity was determined by HPLC on a chiral stationary phase after derivatisation at nitrogen.

ChemInform Abstract: Synthesis of Phosphonic Acid Analogues of Sialic Acids (Neu5Ac and KDN) as Potential Sialidase Inhibitors.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Synthesis of Phosphonic Acid Analogues of Sialic Acids (Neu5Ac and KDN) as Potential Sialidase Inhibitors

Five phosphonic acid analogues of N-acetylneuraminic acid (Neu5Ac) and 3-deoxy-d-glycero-d-galacto-2-nonulosonic acid (KDN) have been synthesized. The synthesis was accomplished using an indium-mediated coupling of N-acetylmannosamine or mannose with dimethyl (3-bromopropen-2-yl)phosphonate in aqueous media. The potential of these phosphonate acid analogues of sialic acids as sialidase inhibitors was evaluated and found to show moderate biological acitivities.

Synthesis of phosphonic acid analogues of sialic acid Neu5Ac

Synthesis of phosphonic acid analogues of sialic acid Neu5Ac

ChemInform Abstract: Enzymes in Organic Chemistry. Part 2. Lipase‐Catalyzed Hydrolysis of 1‐ Acyloxy‐2‐arylethylphosphonates and Synthesis of Phosphonic Acid Analogues of L‐Phenylalanine and L‐Tyrosine.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

ChemInform Abstract: Stereoselective Synthesis of β‐Oxygenated α‐ Hydroxyphosphonates by Lewis Acid‐Mediated Stereoselective Hydrophosphonylation of α‐Benzyloxy Aldehydes. An Application to the Synthesis of Phosphonic Acid Analogues of Oxyamino Acids.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Enzymes in organic chemistry, part 2: Lipase-catalysed hydrolysis of 1-acyloxy-2-arylethylphosphonates and synthesis of phosphonic acid analogues of L-phenylalanine and L-tyrosine

α-Hydroxyphosphonates (±)- 3, prepared by base catalysed addition of phosphites 2 to aldehydes 1, were acylated to give esters (±)- 4. Diethyl 1-acyloxy-2-arylethylphosphonates (±)- 4a, 4b, and 4e were hydrolysed by lipase from Aspergillus niger in a biphasic system to afford ( R)- α-hydroxyphosphonates of low enantiomeric purity. The corresponding diisopropyl phosphonates (±)- 4c, 4f and 4g gave ( S)- α-hydroxyphosphonates with an ee of up to 78%. The absolute configuration of the α-hydroxyphosphonates was assigned by 31P NMR spectroscopy of their ( R)-MTPA-esters. (S)- 3 b and 3e were chemically transformed via their azides to phosphonic acid analogues of L-phenylalanine and L-tyrosine, respectively.

Isosteres of natural phosphates. 6. The preparation and properties of Lysophosphotidic acid

We herein report the first chemical synthesis of phosphonic acid analogues of lysophosphatidic acid. The racemic isosteric analogues, 4-acyloxy-3-hydroxybutyl-1-phosphonic acids, of lyso-phosphatidic acid were prepared by both catalytic and hydride reductions of the 4-acyloxy-3-oxobutyl-1-phosphonic acids, a general method for the preparation of the latter having been reported previously. The lysophosphatidic acids have been found to substrates for lysophosphatidic acid acyl transferase, and may be acylated chemically to yield phosphotidic acids. The latter reaction is of use in the preparation of differentially acylated phosphatidic acids.

Isosteres of natural phosphates. 4. The synthesis of phosphonic acid analogues of phosphatidic acid and acyldihydroxyacetone phosphate

The chemical synthesis of 3,4-diacyloxybutyl-1-phosphonic acids having palmitoyl and oleoyl groups is described. These were prepared by reaction of the appropriate 3,4-diacyloxybutyl-1-bromide with tris (trimethylsilyl) phosphite followed by mild hydrolysis of the trimethylsilyl groups from the phosphonic acid. Also reported is the preparation of 4-palmitoyl-3-oxobutyl-1-phosphonic acid by the acylation of 4-hydroxy-3-oxobutyl-1-phosphonic acid. This latter compounds is an isosteric analogue of acyldihydroxyacetone phosphate.

Phosphonolipids. 23. Synthesis of phosphonic acid analogues of L-alpha-(N-methyl)cephalins.

A procedure for the synthesis of the racemic as well as both enantiomeric forms of phosphonic acid analogues of α-(N-methyl)cephalins has been developed. The synthesis of two representative members of a homologous series of L-α-phosphono(N-methyl)cephalins with saturated aliphatic acid substituents is described in detail. They were obtained by phosphonylating D-α,β-distearin and D-α,β-dipalmitin, respectively, with (N-carbobenzoxy,N-methyl-2-aminoethyl)phosphonic acid monochloride and tri-ethylamine, and removing the protective carbobenzoxy group of the diaeyl-L-α-glyceryl-(N-carbobenzoxy,N-methyl-2-aminoethyl)phosphonates by catalytic hydrogenolysis. The (N-carbobenzoxy,N-methyl-2-aminoethyl)phosphonic acid and its monochloride were prepared by treating the sodium salt of (N-methyl-2-aminoethyl)phosphonic acid with carbobenzoxychloride, and converting the (N-carbobenzoxy,N-methyl-2-aminoethyl)phosphonic acid to the chloride by means of phosphorus pentachloride. α-Phosphono(N-methyl)cephalins, α-(N-methyl)cephalins, and α-cehalins with identical fatty acid substituents have similar melting points, specific rotations, and solubility properties. The α-phosphono(N-ethyl)cephalins can be readily separated from α-(N-methyl)cephalins and α-cephalins by thin-layer chromatography on silica gel H or G.

Phosphonolipids. XXI. Synthesis of phosphonic acid analogues of diether L-alpha-(N,N-dimethyl)cephalins.

A synthesis of phosphonic acid analogues of diether L-α-(N,N-dimethyl)cephalins, viz. di-O-tetradecyl, di-O-hexadecyl, and di-O-octadecyl L-α-glyceryl-(N,N-dimethyl-2-aminoethyl)phosphonate, is described. They were obtained by phosphonylating the appropriate D-α,β-dialkyl glycerol ethers with 2-bromoethylphosphonic acid monochloride and triethylamine at 0°, and treating the reaction products with dimethylamine at 50–55° for 3 days. The procedure is applicable to the synthesis of saturated and unsaturated dialkyl α-(N,N-dimethyl)phosphonocephalins in both their optical active forms.

Phosphonolipids. XXII. Synthesis of phosphonic acid analogues of L-alpha-(N-methyl)cephalins.

Distearoyl and dipalmitoyl L-α-glyceryl-(N-methyl-2-aminoethyl)phosphonates were synthesized by phosphonylating D-α,β-distearin and D-α,β-dipalmitin, respectively, with (N-carbobenzoxy,N-methyl-2-aminoethyl)phosphonic acid monochloride and triethylamine, and removing the protective carbobenzoxy group by catalytic hydrogenolysis.

The synthesis of phosphonic acid analogues of purine ribonucleotides: an exception to the trans rule

The synthesis of phosphonic acid analogues of purine ribonucleotides: an exception to the trans rule

Erratum; Phospholipids. XVI. An alternative method for the synthesis of phosphonic acid analogues of L-α-cephalins

Erratum; Phospholipids. XVI. An alternative method for the synthesis of phosphonic acid analogues of <scp>L-</scp>α-cephalins