ChemInform Abstract: SYNTHESIS OF BISPHOSPHATIDIC ACIDS DERIVATIVES AND THIOANALOGS

Abstract

Die Phosphoglyceride (I) werden zu den entsprechenden Thio‐ bzw. Dithiophosphaten (II) umgesetzt und dann mit den Säurechloriden (III) zu den entsprechenden Thio‐ bzw. Dithiophosphatidsäuren (IV) acetyliert.

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

“…15 The new method for the acylation of glyceroacetals probably merits extensive use. It has already been applied successfully in the synthesis of a series of ester phospholipids I 4 -' 6,26,45,56,57,73,75,87,91,92,106,109,128,[150][151][152][153][154][155] An even simpler version of the synthesis of phosphatidic acids, their thio-analogues, and also their previously unknown seleno-analogues is based on the use of the available bis(trimethylsilyl) l,2-O-isopropylidene-3-glycerophosphite 16 (see below). This silyl phosphite was converted by oxidation (by the addition of oxygen, sulfur, and selenium) into the COC1 18 According to 31 P NMR data, thio-and seleno-phosphatidic acids exist in chloroform solutions in the thiono-and selenonophosphoryl forms.…”

“…30 ' 75 -1OS Thus phosphoramidites have been used to synthesis phosphatidylglycerols (Scheme 62) (see previous page). 75 The neutral benzyl esters of phosphatide and thionophosphatide can be converted into phosphatidylglycerol (thiophosphatidylglycerol) by total debenzylation taking into account the results of other investigations. 1 ' 3 -8 - 10 Another aspect of the synthetic application of glycerophosphoramidites concerns studies on the cyclophosphorylation of bifunctional nucleophiles, in the first place glycols (Scheme 63).…”

“…Thus a convenient method of synthesis of bisphosphatidic and previously unknown thiobisphosphatidic acids from ethyl diglycerophosphite has been developed with the aid of the fundamentally new synthetic solutions examined above [acylation of glycerol derivatives via the acetal bonds and the removal of the alkyl protecting groups by silylation and subsequent hydrolysis (Scheme 31)] 75. …”