Chemoenzymatic synthesis of trans-dihydrodiol derivatives of monosubstituted benzenes from the corresponding cis-dihydrodiol isomers

Enantiopure trans-dihydrodiols have been obtained by a chemoenzymatic synthesis from the corresponding cis-dihydrodiol metabolites, obtained by dioxygenase-catalysed arene cis-dihydroxylation at the 2,3-bond of monosubstituted benzene substrates. This generally applicable, seven-step synthetic route to trans-dihydrodiols involves a regioselective hydrogenation and a Mitsunobu inversion of configuration at C-2, followed by benzylic bromination and dehydrobromination steps. The method has also been extended to the synthesis of both enantiomers of the trans-dihydrodiol derivatives of toluene, through substitution of a vinyl bromine atom of the corresponding trans-dihydrodiol enantiomers derived from bromobenzene. Through incorporation of hydrogenolysis and diMTPA ester diastereoisomer resolution steps into the synthetic route, both trans-dihydrodiol enantiomers of monohalobenzenes were obtained from the cis-dihydrodiols of 4-haloiodobenzenes.     

Urea and thiourea derivatives as low molecular-mass organogelators

The properties of a series of organogels consisting of a urea or thiourea derivative with one or two n-alkyl substitutuents at the nitrogen atoms (a low molecular-mass organogelator (LMOG)) and an organic liquid are described. They include N,N'-dimethylurea, the LMOG of lowest molecular mass (M(W) 88) we are aware of. The efficiencies of the LMOGs, based the diversity of liquids gelated, the minimum amount required for gelation of a liquid at room temperature, and the temporal and thermal stabilities of the gels formed, have been investigated as a function of the number, length, and substitution pattern of their n-alkyl chains. The gels are thermally reversible and require generally very low concentrations (<2 wt %) of an LMOG. Some of the LMOGs with shorter chains are more efficient than their longer chained analogues. The structural and thermodynamic properties of the gels have been examined by IR, DSC, and X-ray diffraction techniques. Polarizing optical microscopic analyses of the gels show that the nature of gelator aggregates depends mainly on the alkyl chain length. Changes in the aggregation ability have been examined systematically by perturbing the molecular structure.     

Isolation of myo-inositol from a mixture of isomers

The transfer reaction of phosphatidylcholine and aqueous solutions of inositols that is catalyzed by phospholipase D is studied. Optimal conditions for synthesis of posphatidylinositol in a water—organicsolvent heterogeneous system are found. Addition of the alcoholic substrate methanol to the reaction medium is demonstrated to liberate myo-inositol from the phosphatidylinositol in hexane—water. Myo-inositol is isolated from a mixture of isomers by carrying out the double transfer reaction using phospholipase D.Mirzo Ulugbek National University of Uzbekistan. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 160–163, March–April, 2000.     

Generation of strong, homochiral bases by electrochemical reduction of phenazine derivatives

Electrochemical reduction of enantiomerically pure amino- and alkoxy-phenazine derivatives forms strongly basic radical anions which give asymmetric induction in the conversion of 3,4-epoxytetrahydrothiophene-1,1-dioxide into the allylic ester with facile regeneration of the phenazine.     

Synthesis of myo-inositol derivatives required for the total synthesis of surugatoxin, prosurugatoxin, and neosurugatoxin

Two myo-inositol derivatives (4) and (5), required for the total synthesis of surugatoxin, prosurugatoxin, and neosurugatoxin, were prepared. Synthesis of (+/-)-2,3-O-cyclohexylidene-4,5-O-isopropylidene-1-O-methoxymethyl-myo-i nositol (4) was achieved from (+/-)-1-O-benzoyl-2,3-O-cyclohexylidene-4,5-O-isopropylidene-myo-inosito l (6) in 4 steps, and (-)-2,3-O-cyclohexylidene-1,4-di-O-methoxymethyl-5-O-[2',3',4'-tri-O-ace tyl- beta-D-xylopyranosyl]-myo-inositol (5) was synthesized from (+/-)-1-O-benzoyl-2,3-O-cyclohexylidene-5,6-O-isopropylidene-myo-inosito l (12) in 7 steps.     

Glucofuranose derivatives as a library for designing and investigating low molecular mass organogelators

We designed and synthesized a class of saccharide-based gelators having three free OH groups in the glucofuranose fragment. The gelating abilities of fourteen compounds were examined to systematically study the influence of the hydrophobic fragment connected to the C2′ carbon. Also the correlation between the saccharide crystal structure and its gelating properties was examined, showing limited usefulness in this particular case. SEM observations were carried out in order to investigate the hierarchical structure of xerogels and changes depending on different gel concentration.     

Novel organogelators based on pyrazine-2,5-dicarboxylic acid derivatives and their mesomorphic behaviors

A series of new low molecular organogelators (LMOGs) with thermotropic mesophase were synthesized via the reaction of 3,6-dimethyl-pyrazine-2,5-dicarboxylic acid with p-alkoxyl anilines. These compounds readily formed stable gels in a variety of organic solvents and their self-assembly behavior, structure–property relationship were investigated by scanning electron microscopy (SEM), X-ray diffraction (XRD), ¹H nuclear magnetic resonance (¹H NMR), Fourier transform infrared spectroscopy (FTIR) and ultra-violet–visible spectroscopy (UV). The results showed a combination of intra-hydrogen bonding, π–π stacking and van der Waals interaction resulted in the aggregation of the organogelators to form three-dimension fibrous networks. The gels formed were multi-responsive to environmental stimuli, such as temperature, fluorinion, and shear stress. More importantly, all the organogelators exhibited thermotropic hexagonal column mesophase as revealed by differential scanning calorimetry (DSC), polarized optical microscopy (POM), and variable temperature XRD studies. A control compound was synthesized and its gelling ability was also checked.     

Selectivity of Candida rugosa lipase in simultaneous separation of skeletal isomers, desymmetrization, and kinetic racemate cleavage of 9-oxabicyclononanediols

The diols 2 and 3, available in one step from cycloocta-1,5-diene, are selectively acetylated at the (R)-centers using Candida rugosa lipase to give the corresponding enantiopure compounds. In contrast, the (S,S)-enantiomer of 11 is transformed under identical conditions. The stereoselectivity of the lipase has been investigated by modeling of the transition state geometries at the active site of the enzyme.     

Nucleoside-based organogelators: gelation by the G-G base pair formation of alkylsilylated guanosine derivatives

2′,3′-O-Isopropylideneguanosine derivatives 1a-c having a bulky alkylsilyl moiety showed excellent gelation ability in alkane solvents. IR spectra of the gel clearly showed the absence of hydrogen bonding interaction at the C(6)O position and, together with a CD study, a G-G base pair formation by double N(2)H?N(3) and additional N(2)H?O(2′) hydrogen bonds was indicated. X-ray diffraction and SEM studies of the xerogel and AFM observation of the transferred gel suggested the formation of a two-dimensional supramolecular assembly 2 nm in thickness. The G-G base pair formation is discussed in terms of the molecular packing in the two-dimensional assemblies.     

Anthracene derivatives and the corresponding dimers with TEMPO radicals

Anthracene derivatives with several TEMPO radicals (2-4, 10) were prepared, and each photodimerization reaction was investigated. Although the photodimerization was unsuccessful in obtaining the dimers of anthracenes 2 and 3, which could be alternatively prepared in a stepwise manner, the photodimers of anthracenes 4 and 10 were available by the direct photoreaction. The dissociation reaction of the dimers proceeded well by heating them in solution to give the corresponding monomers in each case, and thus the reversible system could be constructed in the latter two systems. While no large difference was observed in their magnetic behaviors between the monomer/dimer pair of 4 and 8, an intriguing difference was found in the magnetic behaviors for the pair of 10 and 11 from ferromagnetic interactions in 10 to the variable magnetic interactions in 11 depending on the solvent molecules incorporated in the crystals.     

Novel class of saccharide-based organogelators: glucofuranose derivatives as one of the smallest and highly efficient gelators

Gluco- and allofuranose derivatives, having unprotected three OH groups, were investigated as potential gelators, showing high gelating ability for a variety of organic solvents and result in new consistent class of organogelators. The minimum gelator concentration reaches 0.03%, which is one of the lowest concentrations achieved so far. The correlation between the saccharide crystal structure and its gelating ability was also examined. The SEM pictures of xerogeles obtained from concentrated and diluted gels (1.0-0.03%) show significant differences in μm-scale structure.     

New derivatives of poly-hexafluoropropylene oxide from the corresponding alcohol

Poly-hexafluoropropylene oxide (poly-HFPO) alcohol was prepared by the reduction of the corresponding methyl ester using NaBH_4, NaBD₄, or LiAlH₄ (LAH). This alcohol is a versatile starting material for the preparation of additional interesting compounds. Because of its expected poor nucleophilicity, before attempting additional reactions, we have found it advantageous to prepare a corresponding salt. We have found that the resulting salt behaved like a normal hydrocarbon alkoxide. The reaction of this salt with either acetyl chloride or allyl chloride (or bromide) gave the expected products which proved to be normal nucleophilic substitutions. In addition, the bromination of the allyl ether was studied using NMR and GC/MS techniques.     

The gas phase enthalpies of formation of hydrazine, its methylated derivatives, and the corresponding values for ammonia and its methylated derivatives

Hydrazine and some of its methylated derivatives are highly important species. Despite their molecular simplicity and those of the other methylated derivatives, ammonia, and the corresponding amines, there are significant problems with the literature values of their gas phase enthalpies of formation. We present our high level quantum chemical calculations at the G4 level for all of these species.     

Capillary electrophoretic analysis of the derivatives and isomers of benzoate and phthalate

A capillary electrophoretic method for the analysis of 12 commonly found derivatives and isomers of benzoate and phthalate, including p-toluic acid, p-acetamido and p-hydroxy derivatives of benzoic acid, salicylic acid and its acetyl ester, 2- and 4-isomers of carboxybenzaldehyde, meta-, para-, and ortho-isomers of phthalic acid, and monomethyl terephthalic acid was developed. Capillary electrophoresis (CE) was performed in the free zone electrophoresis mode. Performing CE in 10 mM phosphate buffer, pH 7.0 could separate most of the benzoic acid derivatives except the structural or positional isomers. The positional isomers of phthalic acids could be completely separated with co-addition of alpha- and beta-cyclodextrins. Addition of poly(ethylene glycol) 600 (4%) could further resolve some structural isomers. The CE method developed here is rapid, i.e. complete separation could be achieved in less than 8 min for the nine monoanionic benzoate derivatives and in less than 14 min for the three dianionic phthalate isomers. The new method has good precision and linearity and can be readily applied to real samples for quantitative analysis. It is sensitive and can detect sub-ppm (w/w) level of impurity in real terephthalic samples.     

Synthesis and properties of coumarin-derived organogelators

A new family of coumarin derivatives containing amide group with different alkyl chain lengths was synthesized and their properties as organogelators were evaluated. It was found that the organogelation abilities were not obviously affected by the alkyl spacer length of amide group. Helical morphologies formed either in nonpolar or high polar solvents by most of the gelators. Occurrence of reversible and stereoselective photodimerization of the gel formed by 4-(7′-coumarinoxy)-N-octadecylbutanamide (3a) in cyclohexane was confirmed by ¹H NMR, UV absorption, and fluorescence spectra. The photoreaction of the gel proceeded without any dissolution, but the drastic microscopic changes of gel morphologies accompanied with the irradiation were identified using SEM and AFM investigations.     

Synthesis of anti-2-aryl-4-en-1-ols from the corresponding syn isomers

Russian Journal of Organic Chemistry - Stereoselective synthesis of anti-2-aryl-4-en-1-ols from the corresponding syn isomers was accomplished with 71–83% yields via the Mitsunobu reaction.     

The conversion of halogen-containing polymers to the corresponding hydroxyl derivatives

The direct conversion of poly(epichlorohydrin), poly[3,3-bis(chloromethyl)oxetane], and poly-(vinyl chloroethyl ether) to the corresponding hydroxyl-containing polymers is described. The replacement of the halogen atom in several chlorine-containing polymeric esters by an acetyl group and the subsequent conversion of the latter derivatives to hydroxyl-containing polymers is also described.