Stereoselective Synthesis of (Z)-β-Aryltellurocinnamic Esters

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Enzymatic Regioselective Synthesis of Vinyl Lactose Ester and Its Chemical Polymerization

Transesterification reaction of lactose with divinyladipate in pyridine catalyzed by an alkaline protease from Bacillus subtilis at 50℃ for 3 days gave 6′-O-vinyladipoyl-lactose (yield 35%).Poly (6′-O-vinyladipoyl-lactose) with Mn=21,200,Mw=32,900,Mw/Mn=1.56 could be obtained by chemical polymerization. Poly(vinyl alcohol) containing lactose branch was biodegradable. After 6 days in aqueous buffer(PH7), this alkaline protease could degrade the polymer to an Mn of ca. 2100,Mw/Mn=2.56.     

Stereoselective Synthesis of (Z)-β-Enamido Triflates and Fluorosulfonates from N-Fluoroalkylated Triazoles

N-Fluoroalkylated 1,2,3-triazoles in the presence of triflic acid or fluorosulfonic acid underwent a cascade reaction consisting of triazole protonation, ring opening, nitrogen elimination, sulfonate addition, HF elimination, and hydrolysis to furnish novel trifluoromethanesulfonyloxy- or fluorosulfonyloxy-substituted enamides, respectively, in a highly stereoselective fashion. The vinyl triflates underwent cross-coupling reactions to a variety of substituted enamides and serve as sources of the aminovinyl cations. In reactions with triflic acid, electron-rich triazoles afforded 2-fluoroalkylated oxazoles.     

Palladium-catalyzed stereoconvergent formylation of (E/Z)-β-bromo-β-fluorostyrenes: straightforward access to (Z)-α-fluorocinnamic aldehydes and (Z)-β-fluorocinnamic alcohols

We report here the stereoconvergent formylation of (E/Z)-β-bromo-β-fluorostyrene mixtures with carbon monoxide and sodium formate catalyzed by palladium. Optimization of reaction conditions leads to the corresponding pure (Z)-α-fluorocinnamaldehydes in good yields. The reaction was extended to styrenes bearing electro-attracting or electro-donating groups. The obtained α-fluoroaldehydes were smoothly reduced to the corresponding (Z)-β-fluorocinnamic alcohol by NaBH(4). The reaction could be performed on functionalized substrates as demonstrated by the access to the glucoside of β-fluoroconiferyl alcohol, (Z)-β-fluoroconiferin, a strong inhibitor of lignin polymerization.     

A Stereoselective and Regioselective Total Synthesis of (π)-Trichodiene

Trichodiene (1), a sesquiterpene hydrocarbon, was isolated and characterized by Nozoe and Machida in 1970.¹ Trichodiene (1) has been shown to be the biogenetic precursor of the trichothecane family of sesquiterpenoids characterized by the cytotoxic fungal metabolite (–)-trichodermin (2).^2,3 We recently reported a total synthesis of (±)-trichodiene (1) via lactone 3.⁴ Now, we wish to report another stereoselective total synthesis of (±)-trichodiene (1) via lactone 3 which is highly regioselective.     

Synthesis of ( )-5α-Hydroxy-β-selinene and (-)-5β-Hydroxy-β-selinene

Eudesmanederivativeshavebeendrawingconsiderableattentionduetotheirwidespectrumofbiologicalproperties,particularlyantifeedant,cellgroWthinhibitoryandplantgroWthregulatingactivitiesl'2.Recently,twoepimericeudesmanederivatives( )-5a-hydroxy-6-selinene1and(-)-56-hydroxy-6-selinene2wereisolated3fromtheaerialpartsofCSubtraPicaFMell.,andtheirstructuresweredeterminedbyspectroscopicmethods.Herein,wereportafacilesynthesisofbothtwodiastereomers1and2from( )-dihydrocarvone3infivesteps,usingtheregioselect…     

Total Synthesis of (±) Euphraticol and Its Analogues

Total syntheses of racemic Euphraticol and its analogues are described, they constitute anew and efficient synthetic route to abietane diterpenoids. The key steps are alkylation of lithium eno-late of 8 with iodides in the presence of HMPA.     

β-Galactosidase-Catalyzed Synthesis of Galactosyl Chlorphenesin and Its Characterization

We synthesized galactosyl chlorphenesin (CPN-G) using β-gal-containing Escherichia coli (E. coli) cells in which the conversion yield of chlorphenesin (CPN) to CPN-G reached about 64 % during 12 h. CPN-G was identified and characterized using high-performance liquid chromatography, liquid chromatography-mass spectrometry, Fourier transform-infrared spectrometry, and nuclear magnetic resonance analysis (¹H and ¹³C). We verified that a galactose was covalently bound to a CPN alcohol group during CPN-G synthesis throughout these analyses. In particular, by the hydrolysis of CPN-G using β-gal, it was confirmed that a galactose was bound to CPN. The minimal inhibitory concentration (MIC) results showed that the CPN-G MICs were fairly similar to those of CPN. HACAT cell viability was significantly higher in CPN-G-treated cells than in CPN-treated cells at concentrations of 0.0–20.0 mM. Finally, we accomplished the synthesis of less toxic CPN-G, compared with CPN, using β-gal-containing E. coli cells as whole cells without changes in the MICs against microorganisms.     

A Convenient and Stereospecific Synthesis of (Z)-Benzylidenephthalides

Several 3-benzylidenephthalides have been isolated from natural sources1-2. Some of them are known to possess useful biological activity1 and are also valuable intermediates3 for the synthesis of naturally occurring biologically active compound. Most of the natural 3-benzylidenephthalides exist in the (Z)-configuration. Synthe-tic methods for construction of a 3-benzylidene-phthalide skeleton have been developed4. Some of these methods for synthesizing highly oxygen-functionalized compound…     

Synthesis of (S)-(−)-β-cuparenone and (S)-(−)-cuparene

A short and efficient synthesis of the title compounds is described. (S)-(−)-β-Cuparenone was prepared in 31% yield from p-tolualdehyde and mesityl oxide in eight steps. Absolute stereochemistry was established by means of a diastereoselective cyclopropanation using (R,R)-hydrobenzoin as a recoverable auxiliary.     

Synthesis and Cyclization of N-(4-Phenoxyphenyl)-β-alanines

We have used the reaction of 4-aminodiphenyl ester with acrylic, methacrylic, crotonic, and itaconic acids to synthesize N-substituted -alanines, which undergo ring closure to form derivatives of dihydropyrimidinedione and 4-carboxy-2-pyrrolidinone. We have studied the reactions of acylation and recyclization of the dihydropyrimidinedione ring, and we have synthesized derivatives of 4-carboxy-1-(4-phenoxyphenyl)-2-pyrrolidinone: arylidene hydrazides, 2[(2-oxo-4-pyrrolidinyl-1-(4-phenoxyphenyl)]benzimidazole.     

Regioselective alkylation of 6-(β-methoxyethoxy)guanine to give the 9-alkylguanine derivative

In the presence of lithium hydride 6-(β-methoxyethoxy)guanine reacts regioselectively with 4-bromobutyl acetate to give the 9-alkylguanine derivative.     

Synthesis of lsochroman-4-one and Its Derivatives (Ⅰ)

The medium was modified in the synthesis of the isochroman-4-one.Twenty-one of isochroman-4-one derivatives were synthesized.Among those there were five o-acyl oximes,six mannich bases,four 3-methylene substituted compounds and six pyrimidino and pyrazolo derivatives of isochroman-4-one.Part of the Mannich bases of isochromanone in animal indication was tested     

Synthesis and Characterization of 2-Decyl-DTPA and Its Gd(Ⅲ) Chelate

The present paper covers the synthesis and the characterization of ligand 2-decyl-3, 6, 9-tris(carboxymethyl)-3,6,9-triazaundecan-1,11-dioic acid, H5L, and its Gd(Ⅲ) chelate. The protonation constants for H5L(lgKHi=10.90, 8.50, 4.55, 2.92, 2.20) and the stability constant for GdL2- (lgKGdL2-=22.80) were determined by means of potentiometric titration. They are similar to the corresponding values of DTPA and Gd-DTPA, respectively. The results obtained show that the basicity of the ligand and the stability constant of its Gd(Ⅲ) chelate are not obviously altered after the introduction of a linear chain decyl group into the terminal acetic acid residue of DTPA. The Gd(Ⅲ) chelate may be a potential contrast agent with liver-specificity for magnetic resonance imaging(MRI).     

Synthesis and Characterization of 2-Decyl-DTPA and Its Gd(Ⅲ) Chelate

IntroductionGadoliniumchelatesareveryimportantbecauseoftheirpotentialbiologicalapplicationsintheareaofmagneticresonanceimaging(MRI) .Thegadoliniumchelateofdiethylenetriaminepentaaceticacid(DTPA )wasthefirstMRIcontrastagentinclinicaluse .How ever,Gd DTPA ,asanextracellularcontrastagent,hasnoliver specificity .Theintroductionofanaddi tionallipophilicsubstitutenttoanyoneofthefivemethylenesoftheaceticacidresiduesortoanyoneofthefourcarbonatomsofthebackboneinDTPAmaychangethetissuespecificity…     

Synthesis of (-)-swainsonine and (-)-8-epi-swainsonine by the addition of allenylmetals to chiral α,β-alkoxy sulfinylimines

The asymmetric synthesis of (-)-swainsonine and (-)-8-epi-swainsonine is reported through the addition of either the allenylzinc or the allenyl lithio cyanocuprate reagents derived from [3-(methoxymethoxy)prop-1-ynyl]trimethylsilane to enantiopure α,β-dialkoxy N-tert-butanesulfinylimines derived from d-erythronolactone.     

Synthesis and antimicrobial properties of 3-(β-hydroxyethyl)-1,3-oxazolidins

The possibility of synthesis of 3-(β-hydroxyethyl)-1,3-oxazolidin and its substituted derivatives at position 2 by the condensation-heterocyclization of diethanolamine with certain aldehydes and ketones was examined. The structure of the compounds was identifi ed by NMR spectroscopy. We investigated antimicrobial properties of the synthesized compounds against microorganisms that affect the lube oil M-11 and found a dependence of the antimicrobial properties on the nature of the substituent at position 2 of oxazolidin heterocycle.