ChemInform Abstract: NEW APPROACH TO THE SYNTHESIS OF PHOSPHATIDIC ACIDS AND THEIR ANALOGS

Abstract

Durch Reaktionen der Diglyceride (I) mit Diethylamidodibenzylphosphit, Oxidationen der Phosphite (II) mit Iodosobenzol (oder auch N‐Oxiden) bzw. Sund schrittweise Abspaltung der Benzylgruppen werden die Phosphatidsäuren (V) dargestellt (Ausb.‐Angaben auch im folgenden unvollständig).

Amides of Trivalent Phosphorus Acids as Phosphorylating Reagents for Proton-Donating Nucleophiles

“…The above-outlined general strategy has now been embodied in numerous syntheses of phospholipids of various natures; all of these syntheses were accomplished based on a narrow range of starting compounds and using practically feasible synthetic techniques. , Let us consider the syntheses of phosphatidic acids. They can be prepared from 1,2- or 1,3-acylglycerols, which are made to react with ATPA; this is followed by oxidative reactions and the removal of protective groups, for example, see Scheme . −

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Derivatives of trivalent phosphorus in the synthesis of glycerophosphatides and related phospholipids

“…71 Subsequently triphenyl 72 Phosphorylation by triethyl phosphite has been used for 1,2-diacylglycerols (Scheme 3). 74 Transesterification has been used also for the synthesis of the phosphites of certain other polyols (see, for example, Petrov etal. 72 ).…”

“…124 It has been studied in detail in relation to the phosphorylation of 1,2-O-isopropylideneglycerol 3 and 1,3-0benzylideneglycerol by diethyl(methyl) phosphites in the presence of carbon tetrachloride. 14 ' 15 - 74 As an example, we present the synthesis of diethyl 1,2-isopropylideneglycerophosphate 10 (Scheme 11). The process is based on the use of readily available starting compounds, is carried out under mild conditions, and gives rise to high yields of the target products.…”

“…§ It has been suggested that the simplest of these compounds-acyclic esters -be used to synthesise phosphatidic acids. 74 Thus dibenzyl 1,2-diacylglycerophosphites 12 are oxidised ^ by nitrogen oxides or iodosobenzene with formation of the corresponding dibenzyl phosphates 13 (X = O), which were obtained previously via a much more complex scheme: by the reaction of the silver salts of dibenzylphosphoric acids with glycerol 1,2-diacylhalohydrins which are difficult to obtain and inconvenient to work with. 1 ' 3 ' 8 -10 Dibenzyl phosphates 13 (X = O) are subsequently converted into the phosphatidic acids 14 (X = O).…”

“…Thus it has been shown that the tetraethyldiamide derivative of 1,2-distearoylglycerol 7 is readily converted on treatment with two equivalents of benzyl alcohol into the neutral phosphite 12, which is readily converted into the phosphatidic acid (see above). 74 If the benzylolysis of the phosphorodiamidite 7 is carried out using an equivalent amount of alcohol, then selective monophosphorylation takes place. After oxidation and the removal of the protecting group, the product 24 was converted into an acid phosphoramidate-a representative of a rare class of phospholipids (Scheme 45 Readily available and effective reagents-nitrogen(II) oxides and iodosobenzene-were used as oxidants in the schemes described above.…”