Characterization of four diol dehydrogenases for enantioselective synthesis of chiral vicinal diols

Enantiopure vicinal diols are important building blocks used in the synthesis of fine chemicals and pharmaceutical compounds. Diol dehydrogenase(DDH) mediated stereoselective oxidation of racemic vicinal is an efficient way to prepare enantiopure vicinal diols. In this study, four new bacterial DDHs(AnDDH from Anoxybacillus sp. P3 H1 B, HcDDH from Hazenella coriacea, GzDDH from Geobacillus zalihae and LwDDH from Leptotrichia wadei) were mined from the GenBank database and expressed in E. coli T7.The four DDHs were purified and biochemically characterized for oxidation activity toward(R)-1-phenyl-1,2-ethanediol, with the optimal reaction condition of pH9.0(AnDDH), 10.0(HcDDH) and 11.0(GzDDH and LwDDH) and the temperatures at 40 ℃(AnDDH), 50 ℃(HcDDH) and 60 ℃(GzDDH and LwDDH), respectively. The four enzymes were stable at the pH from 7.0 to 9.0 and below 40 ℃.Kinetic parameters of four DDHs showed that the HcDDH from Hazenella coriacea had high activity toward a broad range of vicinal diols. A series of racemic vicinal diols were successfully resolved by recombinant E. coli(HcDDH-NOX) resting cells co-expression of an NADH oxidase(NOX), affording(S)-diols and(1 S, 2 S)-trans-diols in ≥99% ee. The synthetic potential of HcDDH was proved by E. coli(HcDDH-NOX) via kinetic resolution of racemic trans-1,2-indandiol on a 100 ml scale reaction,(S, S)-trans-1,2-indandiol was prepared in 46.7% yield and >99% ee. In addition, asymmetric reduction of four α-Hydroxy ketones(10–300 mmol·L^(-1)) by E. coli(HcDDH-GDH) resting cells resulted in >99% ee and69–98% yields of(R)-vicinal diols. The current research expands the toolbox of DDHs to synthesize chiral vicinal diols and demonstrated that the mined Hc DDH is a potential enzyme in the synthesis of a broad range of chiral vicinal diols.

Preparation for Supramolecular Complexes of Chiral Diols BDPDD, DMBDPD and BINOL with Some Prochiral Compounds

Interaction between chiral diols BDPDD, DMBDPD and BINOL with prochiral compounds was examined and some new supramolecular complexes were prepared. It was found that these chiral hosts could include prochiral guests, a, b-unsaturated compounds or piper- azinedione derivatives to give inclusion crystals in different molar ratio. Formations of these supramolecular complexes were characterized by the data of IR and 1H NMR spectra.

Selective monotetrahydropyranylation of symmetrical diols using P_20_5/Si0_2 under solvent-free conditions and their depyranylation

Selective protection of one of the hydroxyl group in 1, n-symmetrical diols is achieved by P2O5/SiO2-catalyzed reaction of the diol with dihydropyran under solvent-free conditions at room temperature. This selective protection is simple and it occurred under economically cheap conditions in high yield. The deprotected diol is simply obtained by refluxing of this compound in methanol using the same catalyst without any byproduct formation or additional purifications.

Synthesis and characterization of new polyesters based on 2,5-bis[(4-chloro carboxyanilino)carbonyl]pyridine and aromatic diols

Six new polyesters 7a-f were synthesized through the solution polycondensation reaction of diacid chloride 5 with six aromatic diols 6a-f in N,N-dimethyl acetamide(DMAc) as solvent in the presence of pyridine as base.The polycondensation reaction produced a series of novel polyester containing pyridyl moiety in the main chain in high yields with inherent viscosities between 0.35 and 0.54 dL/g.The resulted polymers were fully characterized by means of FT-IR spectroscopy,elemental analyses,inherent viscosity ...

Spatial Distributions and Potential Sources of Long Chain(C_(30),C_(32)1,15-)Alkyl Diols in Surface Sediments from Eastern China Marginal Seas

Long chain alkyl diols have shown important potential for the reconstruction of sea surface temperature,productivities and upwelling conditions in marine or lacustrine environments.However,little is known about the distribution and sources of the diols in eastern China marginal seas(CMS),which are areas of important organic carbon sink.Here the contents of C_(30) and C_(32)1,15-diols were analyzed in 181 surface sediments from eastern CMS.The similar distribution pattern and strong linear correlation between C_(30) and C_(32) diols indicated that they had similar biological source,with a dominance of C_(30) diol.Their contents ranged from 7-2726 ng g^(-1) for C_(30) diol and 5-669 ng g^(-1) for C_(32) diol,and both showed higher values mainly in the mud area of the Yellow Sea,while the TOC normalized contents showed a more obvious seaward increasing trend.The similar distribution pattern and significant positive correlation between diols and the other marine biomarkers(brassicasterol,dinosterol,C_(37) alkenones) indicated C_(30) and C_(32) diols in eastern CMS were mainly from marine algae.This conclusion was also supported by principal component analysis(PCA).Our results also showed that sediment diol contents were generally related to marine productivity,suggesting that diols could be applied for marine productivity reconstruction in eastern CMS.

Elimination Reaction of α,ω-Diols by Magnesium

1,3-Propanediol, 1,4-butanediol or 1,5-pentanediol reacts with magnesium to form corresponding magnesium alkoxides, which elindnate water with the formation of cyclic ethers and, respectively, allyl alcohol, 3-buten-1-ol and 4-penten-1-ol.

Selective Monoprotection of Symmetrical Diols in a Flow Reactor

Desymmetrization reactions provide a powerful approach for the construction of complex molecules. Various methods have been developed for the selective monoprotection of symmetrical diols;however, their application to large-scale operations is limited. In this study, the monotetrahydropyranylation of symmetrical diols in a flow reactor has been developed, whereby the length of the flow reactor tube and the amount of acid were optimized. A higher selectivity for the monoprotected derivative was observed when the reaction was performed in a flow reactor compared with that observed in a conventional batch experiment. The efficient flow method developed herein can be applied to large-scale synthesis by numbering up the flow reactor without affecting the selectivity and yield. Since monoprotection can be achieved without using a large excess of diol, our developed flow method is effective when expensive diol must be used.

Facile Preparation of 1,2-Diols from Chalcones: An NMR Spectroscopy and X-Ray Crystallography Study

Structures of 2-(naphthalen-2-ylmethyl)-2,3-dihydro-1H-indene-1,2-diol (C20H18O2), compound 1 and 1-(3,4-dimethoxyphenyl)-3-methoxy-3-(4-nitrophenyl)propane-1,2-diol chloroform (C18H21NO7·CHCl3) compound 2 were established by spectral and X-ray diffraction studies. Compound 1 crystallizes in the orthorhombic space group P212121 with unit cell parameters a = 5.2177 (6), b = 13.903 (2), c = 21.121 (2) A, Z = 4. Compound 2 crystallizes in the triclinic space group P-1 with unit cell parameters a = 9.238 (1), b = 9.879 (1), c = 12.636 (1) A, α = 102.004 (1), β = 92.356 (1), γ = 90.779 (1)o, Z = 2. These two new molecules arise from a facile preparation of 1,2-diols from chalcones and have been fully characterized. Based on the crystallographic information obtained for compound 1, the relative configuration for the chiral centers is 1S and 2S. In structure 1, both hydroxyl groups adopt an anti-conformation with a torsion angle O1-C1-C2-O2 value of 93.1 (2)o [in molecule 2, both hydroxyl groups adopt a trans-conformation with a torsion angle O1-C1-C2-O2 value of -171.0 (2)。]. In both structures, the molecules in the crystal are linked by intermolecular hydrogen bonds O-H···O and C-H···O interactions and adjacent molecules are interconnected by intermolecular weak C-H···π and C-H···Cl interactions which give additional support to molecular packing stability.

Green Synthesis of Chemically Recyclable Polyesters via Dehydrogenative Copolymerization of Diols

Preparation of chemically recyclable polyesters by ring-opening polymerization(ROP)has made a considerable progress over the past few years.However,this method involves cumbersome synthesis and minimal functional diversity of cyclic monomers.Therefore,it is of great significance to develop novel polymerization methods for direct polymerization of commercially available monomers to prepare recyclable polyesters with versatile functionalities.In present work,we report dehydrogenative copolymerization of commercialα,ω-diols to afford high molecular weight chemically recyclable aliphatic copolyesters(65.7 kg·mol^(-1))by using commercially available Milstein catalyst precursor.The thermal properties of the obtained copolymers could be finely tuned by simply adjusting the feeding ratio of two monomers.The incorporation of aliphatic or aromatic rings into polyester mainchain via copolymerization of 1,10-decanediol with 1,4-cyclohexanedimethanol and 1,4-benzenedimethanol could significantly improve the thermal properties of the resulting copolymers.More importantly,the obtained copolyesters were able to completely depolymerize back to original diols via hydrogenation by the same catalyst in solvent-free and mild conditions,thus offering a green and cost-effective route toward the preparation of widely used polyesters.

Bifunctional fluorescent probes for hydrogen peroxide and diols based on a 1,8-naphthalimide fluorophore

This report discloses a series of naphthalimide-based bifunctional fluorescent probes for hydrogen peroxide and diols.As a result,these molecules not only demonstrated high turn-on fluorescent response and good selectivity towards hydrogen peroxide over other relevant reactive oxygen species,but also displayed different responses to diols.Therefore,these fluorescent probes could be served as sensitive,selective and practical chemosensors for both hydrogen peroxide and diols under physiologicallike conditions.

Asymmetric reduction of α-hydroxy aromatic ketones to chiral aryl vicinal diols using carrot enzymes system

Asymmetric reduction of ct-hydroxy aromatic ketones was carded out by using carrot enzymes system, yielding corresponding chiral vicinal diols with special functional groups. The optimum reaction conditions were obtained after investigation of various influencing factors. Chiral aryl vicinal diols were produced with good yields and excellent enantiomeric excesses under appropriate conditions. Meanwhile, the steric factors and electronic effects of the substituents on the aromatic ring were shown to have an interesting influence on both yield and enantioselectivity.

Synthesis of Polycarbonate Diols（PCDLs） via Two-step Process Using CH3COONa as an Effective Catalyst

Polycarbonate diols（PCDLs） with a number average molecular weight（M,） of 2800 and a narrow polydispersity index（PDI=1.33） were synthesized from dimethyl carbonate（DMC） and 1,4-butarlediol（BD） via a two-step process. The influences of the molar ratios of DMC to BD in the feedstock, polycondensation temperature and polycondensation time on the PCDLs preparation were studied. CH3COONa showed the best catalytic performance among the catalysts studied. The highest BD conversion of 73.8% and PCDLs yield of 64.7% were achieved under its optimum reaction conditions. Furthennore, based on the results of 1^H NMR, the relationships between the ratio of end groups （--OCH3/-OH） of oligomers, the Mn and chain-end constitute of resultant polycarbonates were also investigated. The results indicate that PCDLs can be synthesized when the oligomers mostly bear hydroxyl end groups. In contrast, it was impossible to prepare PCDLs when the oligomers were enriched with methyl carbonate end groups,

HPLC检测他克莫司软膏剂中他克莫司的含量

目的建立并验证高效液相色谱法检测他克莫司软膏中他克莫司的含量。方法 Ultimate XB-Di-ol色谱柱(4.6 mm×250 mm,5μm);流动相为正己烷-正丁基氯-乙腈;检测波长225 nm;流速1.7 mL/min;温度:室温。结果他克莫司的线性范围Y=2 600.7X-583.82,相关系数为0.999 9,线性范围为2 mg/L^200 mg/L,平均回收率为98.97%,RSD为0.47%。结论本方法简便、灵敏、准确、重现性好、专属性强,可用于药厂对他克莫司软膏剂中他克莫司的测定。

Aqueous-Phase, Palladium-Catalyzed Suzuki Reactions under Mild Conditions

Water-soluble ionic liquid-supported diols have been used as phosphine-free ligands in Suzuki couplings of aryl idides/bromides/chlorides under mild conditions in aqueous solvent. It was found that 2,2-bis((1-hexylimidazolium)-mehyl) propane-1,3-diol hexafluorophosphate (4) in combination with palladium (II) salts gave the most significant catalyst. Suzuki couplings of aryl iodides/bromides occurred efficiently at room temperature in water/acetonitrile. Notably, the reactions of hydrophilic aryl bromides gave high yields in neat water. The catalyst PdCl2-4 was recycled five times in Suzuki couplings in water before catalyst activity began to significantly drop. The average yield of five cycles was >95% per cycle.

Ent-Kauran-16β,17-diol碳信号的修正及其意义

作者针对文献关于 ent- kauran- 16 β,17- diol( )碳信号指认有误的问题 ,用化学合成方法和 2 D-NMR技术对 的结构进行全面分析和论证 ,首次归属了每个氢质子的信号 ,并再次证实其结构中的 C- 1、C- 7和 C- 14互为颠倒 ,该研究对 ent-

One-pot-synthesis of novel cinchonine-based phosphites

Cinchonine was employed as backbone for the synthesis of novel phosphite compounds with diol substituents. These monophosphinites were provided in one pot with the yields ranged from 63% to 75%. Their structures were confirmed by NMR spectroscopy and HRMS. C 2009 Sheng Yong Zhang. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.

Synthesis of Chiral Amino Cyclic Phosphoric Acids

Chiral amino cyclic phosphoric acids, 5-amino-2-hydroxy-4-(4-nitrophenyl)-1,3,2-dioxaphosphorinane 2-oxide and 2-hydroxy-4-(4-methylsulfonylphenyl)-5-phthalimido-1,3,2-dioxaphos phorinane 2-oxide are synthesized in good over yields (64.2%and 72.8%respectively) from 2-amino-1-aryl-1,3-propanediols. The different reaction conditions are necessary in hydrolysis reactions of amino cyclic phosphonyl chlorides.

Investigation of Synthesis of Functionally Substituted Endiines and Their Chemical and Microbiological Conversion

The methods of preparation of endiine and endiallene diols by interaction of cis-1,4-dibrombutene and cis-1,4-dichlor-rbutene with monosubstituted acetylene alcohols in presence of the catalytic systems consisting of one-iodide copper, triethylamine and K2СО3 in a medium of dimethylformamide have been developed. It has been shown that unlike 1,4-dibrombutene, the nucleophilic substitution reaction with 1,4-dichlorbutene proceeds by acetylene-allene isomerization with formation of endiallene diols. It has been established that the endiine diols can be used in thin organic synthesis (in the reactions of oxidation, splitting, dehydration, epoxidation, hydrolysis, 1,2-cycloaddition and hypochlorination) with the aim of preparation of practically useful substances. It has been revealed during hydrolysis of epoxide compounds by the chemical and microbiological methods that in the course of microbiological hydrolysis (Aspеrgillus niger), the optically active trans-structured diols are formed.

Synthesis of isosorbide-based polycarbonates via melt polycondensation catalyzed by quaternary ammonium ionic liquids

A series of quaternary ammonium ionic liquids(ILs)were synthesized and employed as catalysts for the production of poly(isosorbide carbonate)(PIC)from diphenyl carbonate and isosorbide via a melt polycondensation process.The relationship between the anions of the ILs and the catalytic activities was investigated,and the readily‐prepared IL tetraethylammonium imidazolate(TEAI)was found to exhibit the highest catalytic activity.After optimizing the reaction conditions,a PIC with a weight‐average molecular weight(Mw)of25600g/mol was obtained,in conjunction with an isosorbide conversion of92%.As a means of modifying the molecular flexibility and thermal properties of the PIC,poly(aliphatic diol‐co‐isosorbide carbonate)s(PAIC)s were successfully synthesized,again using TEAI,and polymers with Mw values ranging from29000to112000g/mol were obtained.13C NMR analyses determined that the PAIC specimens had random microstructures,while differential scanning calorimetry demonstrated that each of the PAICs were amorphous and had glass transition temperatures ranging from50to115°C.Thermogravimetric analyses found Td‐5%values ranging from316to332°C for these polymers.Based on these data,it is evident that the incorporation of linear or cyclohexane‐based diol repeating units changed the thermal properties of the PIC.

Cytotoxicity of Benzo(a)pyrene 7,8-dihydrodiol on Genetically Engineered V79 Chinese Hamster Cells Expressing Rat Liver Cytochrome P450 1A1

To develop well defined in vitro cell system to test cytotoxicity of a number of model toxins, genetically engineered V79 Chinese hamster fibroblasts expressing isoenzymes of cytochrome P4501A1 XEM2 cells and V79 cells (parental), which lack cytochrome P450 enzyme activities, were used as controls. The cytotoxic effect of trans 7,8 dihydrbenzo(a)pyrene (BP 7,8 diol) on the parental cells V79 and V79 derived XEM2 cells were evaluated by two methods for cell viability. The data obtained expressed that BP 7,8 diol ranging from 1.0 μmol·L 1 to 5.0 μmol·L 1 in concentrations incubated for 24 h showed a strong cytotoxic effect in XEM2 cells (expressing rat cytochrome P4501A1) in a concentration dependent manner. Time dependent decrease for survival of XEM2 cells was also observed at 2.5 μmol·L 1 concentration. Likewise, BP 7,8 diol did not alter the survival of the parental cells V79 under the same condition. This study also showed that α naphthoflavone (αNF), a well known inhibitor of cytochrome P4501A1 might alter BP 7,8 diol induced cytotoxicity in the XEM2 cells. Our results suggested that cytochrome P4501A1 is responsible for BP 7, 8 diol induced cytotoxicity.