New approach to nonracemic 1-alkylamino-3-aryloxypropan-2-ols belonging to β-blockers via cyclic sulfites

Nonracemic -blockers, viz., (S)-propranolol and (S)-timolol, were prepared from (S)-glycidol in three steps consisting in the reaction with SOCl₂ followed by the reaction of the resulting (4S)-4-chloromethyl-2-oxo-1,3,2-dioxathiolanes with the corresponding phenol and the final cleavage of (4R)-aryloxymethyl sulfites under the action of amines in DMF.     

Reactions of 4-chloromethyl-1,3,2-dioxathiolane 2-oxides with sodium phenoxide. A reinvestigation

The reactions of 4-chloromethyl-1,3,2-dioxathiolane 2-oxides with PhONa in EtOH are accompanied by ring opening under the action of the ethoxide ion rather than leading to a rearrangement of the starting molecule as has been assumed previously. Under conditions precluding competition with other nucleophiles, the phenoxide anion smoothly replaces the chlorine atom in chloromethyl-substituted cyclic sulfites. Published inIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1774–1777, October, 2000.     

New reaction of glycidols with oxalyl chloride and phosgene—an approach to cyclic esters

2,3-Epoxy alcohols (glycidols) react with carboxylic acid dichlorides to form cyclic esters of 3-chloro-1,2-diols. The reaction proceeds with complete retention of the configuration of the C(2) atom of the initial glycidol and with predominant (but not complete) inversion of the configuration of the C(3) atom in the final heterocycle. Translated fromIzvestiya Akademii Nuak. Seriya Khimicheskaya, No. 11, pp. 2110–2114, November, 1999.     

Chiral para-alkyl phenyl ethers of glycerol: synthesis and testing of chirality driven crystallization,liquid crystal,and gelating properties

A series of enantiopure and racemic p-alkylphenyl glycerol ethers 1a–k were synthesized. A new, sensitive, and pictorial method of comparison of the IR spectra of solid enantiopure and racemic samples was developed to obtain preliminary information on the crystallization types of these compounds. In order to detect the subtle differences in the organization of the chiral solid phase, a new easily implemented approach, based on a chromatographic measuring of the relative abundance of the enantiomers in a single solution in equilibrium with a solid sample of arbitrary (0 < ee < 1) composition, is reported. One new conglomerate compound (Alk = n-Pr) and one borderline case (Alk = n-Bu) are disclosed. Higher members of the series of 1 (starting with an n-Bu derivative) are turned into liquid crystals upon melting; no significant differences between racemic and non-racemic samples were found. Only enantiopure methyl-, n-butyl, n-pentyl, n-hexyl, and n-heptyl substituted 1 were able to form supramolecular gels in hydrocarbon solvents; all racemic ethers 1 did not show such ability.     

New approach to cyclic sulfites and sulfates through reactions of sulfur oxychlorides with glycidols

Reactions of 2,3-epoxyalcohols (glycidols) with thionyl chloride or sulfuryl chloride afford cyclic sulfites or sulfates, respectively. These reactions yield predominantly 4-chloroalkyl-1,3,2-dioxathiolane oxides. The configuration of the C(4) atom in the latter compounds exactly corresponds to that of the C(2) atom of the parent glycidol, whereas the configuration of the exocyclic atom is almost completely reversed with respect to that of the C(3) atom of the precursor. Published inIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1586–1593, September, 2000.     

Synthesis of enantiomerically pure 3-aryloxy-2-hydroxypropanoic acids,intermediate products in the synthesis of cis-4-Aminochroman-3-ols

Oxidation of accessible (R)-3-chloropropane-1,2-diol to (R)-3-chloro-2-hydroxypropanoic acid and subsequent reaction of the latter with ortho-substituted sodium phenoxide gave a number of enantiomerically pure 3-aryloxy-2-hydroxypropanoic acid which are intermediate products in the synthesis of nonracemic 4-aminochroman-3-ols.