Synthesis of 1,2-O-Isopropylidene Glycero-Thiolo-(Dithiolo)-Phosphohomocholines. A New Thion-Thiol Isomerization of Alkylene Phosphorothioates

Nifantyev, E. E.; Predvoditelev, D. A.; Rasadkina, E. N.; Bekker, A. R.

doi:10.1080/03086648708074314

Cited by 11 publications

(3 citation statements)

References 8 publications

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“…This indicates that the process is accompanied by the thione-thiol isomerization. Analogous isomerizations were observed previously in the synthesis of other thio phospholipids [10,11]. The 1 H NMR spectrum of VII retained signals from protons in the tricyclic moiety, and new signals appeared due to protons in the trialkylammonium cation.…”

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Synthesis of first phospholipids from 2,2,6,6-tetrakis(hydroxymethyl)cyclohexanol

et al. 2004

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A procedure has been developed for the synthesis of previously unknown thio phospholipids and cationic ammonium amidophosphorus lipids on the basis of 2,2,6,6-tetrakis(hydroxymethyl)cyclohexanol. Model phospholipids have been prepared using phosphorus-containing cyclic compounds. * For short communication, see [1]. Glycerophospholipids persistently attract attention of researchers [2, 3]. However, phospholipids based on aliphatic polyols have been studied poorly. Up to now, only a few examples of such compounds have been synthesized from aliphatic polyols, in particular from 1,2,4-butanetriol [4], 1,2,5-pentanetriol [5], tris-and tetrakis(hydroxymethyl)alkanes [6, 7], xylitol [8], and ribose [9]. Among the prepared phospholipids there were no compounds having structural fragments of aliphatic carbocyclic polyols. On the other hand, phospholipids whose molecules possess an additional rigidity factor should be characterized by a specific steric structure, and they may be important models for studies in various fields of physical and chemical biology and medicine.The goal of the present work was to synthesize previously unknown thio phospholipids and cationic ammonium phosphoramide lipids having a 2,2,6,6-tetrakis(hydroxymethyl)cyclohexanol moiety as structural fragment. In the first step of our study, 2,2,6,6-tetrakis(hydroxymethyl)cyclohexanol (I) was brought into reaction with acetone to protect four hydroxy groups therein. As a result, two isomeric acetals II and III were obtained (Scheme 1). The reaction was performed in the presence of a catalytic amount of anhydrous p-toluenesulfonic acid with simultaneous removal of the liberated water by azeotropic distillation. Acetals II and III differed in the chromatographic mobility, and we succeeded in separating them by column chromatography on silica gel. Moreover, compound III was less soluble in organic solvents; therefore, products II and III can also be purified by recrystallization. The major product was compound II (yield 65%), while the yield of III was as low as 4.8%.The structure of compounds II and III was confirmed by the 1 H NMR spectra. In the spectrum of bis-acetal II, protons of the geminal methyl groups appeared as singlets at δ 1.35 and 1.45 ppm, methylene protons of the cyclohexane fragment gave a multiplet at δ 1.39 ppm, and the singlet at δ 4.28 ppm was assigned to the 1-H proton. The unsymmetrical structure of compound II follows from the spectral pattern formed by signals from axial and equatorial protons in the 1,3-dioxane rings, which were located at δ 3.12 (d), 4.10 (d) and 3.74 (d), 3.95 ppm (d) with the coupling constants 2 J(ax-eq) = 11.9 and 10.99 Hz, respectively. Scheme 1. OH OH HO OH OH

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Synthesis of first phospholipids from 2,2,6,6-tetrakis(hydroxymethyl)cyclohexanol

et al. 2004

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“…The phosphite ( III ) formed was converted into thiophosphate ( IV ) and selenophosphate ( V ) [24,25] by the treatment with sulfur or selenium without isolation and purification (Scheme 2). The reactions were carried out by boiling in anhydrous benzene for 2 h; note that, at room temperature, they completed for 8-12 h. The thio-and selenophosphates ( IV ) and ( V ) were isolated by chromatography on silica gel.…”

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The Synthesis of Thio- and Selenoanalogues of Phospholipids on the Basis of 2-Butyl-2-Hydroxymethyl-1,3-Propanediol

Савин

Kutsemako

2005

Russ J Bioorg Chem

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New analogues of nonglycerol polyol phospholipids were prepared on the basis of 1,1,1-trimethylolethane. Amidophosphites and cyclophosphites of the isopropylidene derivative of this polyol were intermediates in the syntheses. They were treated with sulfur or selenium. Phosphoacetals were converted into lipids by the direct acylation with higher fatty acid chlorides. The triol bicyclophosphite was also used in the lipid syntheses. It was directly acylated at the oxygen atom, the resulting acylpolyol of chlorophosphite was then converted into phospholipids by alcoholysis and subsequent treatment with sulfur.

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“…Bis(O,O-ethylene phosphorothioate) VIII was isolated as an unstable oily substance, while six-membered cyclic thiophosphates IX and X were crystalline products which can be stored for several months in an inert atmosphere without appreciable decomposition. The formation of S-alkyl phosphorothioate XIIb indicates that the reaction of trimethylamine with compound IX is accompanied by thionethiol isomerization [5]. erythritol were extensively studied with a view to obtain surface-active dendrimers [3].…”

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10.1007/s11178-008-3011-6

2010

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A number of cyclic diphosphites were synthesized on the basis of an accessible diol, 1,3 : 1′,3′-di-Obenzylidenedipentaerythritol. The resulting diphosphites were converted into complex covalent and coordination organophosphorus compounds.We recently synthesized first representatives of complete esters derived from dipentaerythritol and phosphorous acid and estimated prospects in their application as ligands for the preparation of coordination compounds of platinum subgroup metals [1]. While developing studies in this line, we made an attempt to build up structurally related systems containing only two phosphite moieties located symmetrically with respect to the central ether oxygen atom. For this purpose we examined phosphorylation of 1,3 : 1′,3′-di-O-benzylidenedipentaerythritol (I) as a mixture of configurational isomers. A procedure for the synthesis of compound I was developed by us previously [2]. As phosphorylating agents we used accessible di-and trimethylene phosphorochloridites II-IV which are highly reactive at 0°C in the system dioxane-pyridine. The yield of target phosphites V-VII ranged from 59 to 80% (Scheme 1). The progress of the reactions was monitored by 31 P NMR spectroscopy (δ P 122-133 ppm). Diphosphites V-VII were purified by passing solutions of the crude products through a layer of silica gel. All tervalent phosphorus compounds V-VII were stable on storage at room temperature in an inert atmosphere. Among these, compounds VI and VII were the most stable.The 1 H NMR spectra of phosphites V-VII contained signals from all protons present in the assumed structures. Compounds V-VII displayed in the spectra signals from methylene protons at δ 3.30-3.39 ppm, a broadened singlet from the CHC 6 H 5 protons at δ 5.45 ppm, aromatic proton signals in the region δ 7.36-7.47 ppm, and doublets from the CH 2 OP protons at δ 4.

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Synthesis of 1,2-O-Isopropylidene Glycero-Thiolo-(Dithiolo)-Phosphohomocholines. A New Thion-Thiol Isomerization of Alkylene Phosphorothioates

Cited by 11 publications

References 8 publications

Synthesis of first phospholipids from 2,2,6,6-tetrakis(hydroxymethyl)cyclohexanol

Synthesis of first phospholipids from 2,2,6,6-tetrakis(hydroxymethyl)cyclohexanol

The Synthesis of Thio- and Selenoanalogues of Phospholipids on the Basis of 2-Butyl-2-Hydroxymethyl-1,3-Propanediol

10.1007/s11178-008-3011-6

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