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1.
Haruo Yamashita Kenyu Shibata Nobuaki Yamakoshi Yuichiro Kurosawa Hiromu Mori 《Bioscience, biotechnology, and biochemistry》2013,77(3):505-509
Microbial 16β-hydroxylation of some steroids with Wojnowicia graminis, Corticium centrifugum and Bacillus megaterium has been reported, but not 16β-hydroxylation of normal 17-oxo steroids with Aspergillus niger. This time, we tried microbial transformation of dehydroepiandrosterone with this fungus, and obtained 4-androstene-3,17-dione, 17β-hydroxy-4-androstene-3,16-dione, 16β,17β-dihydroxy-4-androsten-3-one and a new compound, 16β-hydroxy-4-androstene-3,17-dione. This new compound was also obtained by the fermentation of 4-androstene-3,17-dione and testosterone. 相似文献
2.
F. V. Drozdov V. P. Timofeev A. Yu. Misharin 《Russian Journal of Bioorganic Chemistry》2006,32(1):96-98
3β-Acetoxy-20-oxomethylpregn-5-ene and 3β-acetoxy-20-hydroxymethylpregn-5-ene were synthesized from (22R, 23R)-sitost-5-ene-3β,22,23-triol in 66% overall yields. 相似文献
3.
l-Deoxy-l-l-proIino-d-fructose was isolated from flue-cured tobacco leaves in crystalline form. The structure was confirmed by comparison with synthetic compound. 相似文献
4.
Mucor piriformis was used to study the mode of transformation of 16-dehydroprogesterone (I, pregna-4, 16-diene-3, 20-dione) and 17-hydroxyprogesterone (II, 17-hydroxypregn-4-ene-3, 20-dione). Biotransformation products formed from I were 14-hydroxypregna-4, 16-diene-3, 20-dione (Ia), 7, 14-dihydroxypregna-4, 16-diene-3, 20-dione (Ib), 3, 7, 14-trihydroxy-5-pregn-16-en-20-one (Ic), and 3, 7, 14-trihydroxy-5-pregn-16-en-20-one (Id). Metabolites Ic and Id appear to be hitherto unknown. Time-course studies suggested that the transformation is initiated by hydroxylation at the 14-position (Ia) followed by hydroxylation at the 7-position (Ib). Microsomes (105,000 g sediment) prepared from 16-dehydroprogesterone-induced cells hydroxylate I to its 14-hydroxy derivative (Ia) in the presence of NADPH. Incubation of Ia with the organism resulted in the formation of Ib, Ic and Id. Biotransformation products formed from compound II were 17, 20-dihydroxypregn-4-en-3-one (IIa), 7, 17-dihydroxypregn-4-ene-3, 20-dione (IIb), 6, 17, 20-trihydroxypregn-4-en-3-one (IIc) and 11, 17, 20-trihydroxypregn-4-en-3-one (IId). Time-course studies indicated that IIa is the initial product formed, which is further hydroxylated either at the 6 or 11 position. Incubation of IIa with the organism resulted in the formation of IIc and IId. Reduction of the 4-en-3-one system and 20-keto group has not been observed before in organisms of the order Mucorales. In addition, M. piriformis has been shown to carry out hydroxylation at the C-6, C-7, C-11 and C-14 positions in the steroid molecules tested. 相似文献
5.
Microbial transformation experiments were conducted with the antitumor lactone withaferin-A. NRRL 1393 transformed withaferin-A () to 15β-hydroxywithaferin-A () and 12β-hydroxywithaferin-A (). The hydroxylated metabolites were isolated by solvent extraction and were purified by column and thin-layer chromatography. Structures of the hydroxylated metabolites were determined by protonand carbon-13 NMR, IR and mass spectral analyses, and by the preparation of acylated derivatives. Compounds and inhibited the growth and biochemical functions of grown P-388 lymphocytic leukemic cells. 相似文献
6.
《Phytochemistry》2012
Candol A (7β-hydroxy-ent-kaur-16-ene) (6) is efficiently transformed by Gibberella fujikuroi into the gibberellin plant hormones. In this work, the biotransformation of its acetate by this fungus has led to the formation of 7β-acetoxy-ent-kaur-16-en-19-oic acid (3), whose corresponding alcohol is a short-lived intermediate in the biosynthesis of gibberellins and seco-ring ent-kaurenoids in this fungus. Further biotransformation of this compound led to the hydroxylation of the 3β-positions to give 7β-acetoxy-3β-hydroxy-ent-kaur-16-en-19-oic acid (14), followed by a 2β- or 18-hydroxylation of this metabolite. The incubation of epicandicandiol 7β-monoacetate (7β-acetoxy-18-hydroxy-ent-kaur-16-ene) (10) produces also the 19-hydroxylation to form the 18,19 diol (20), which is oxidized to give the corresponding C-18 or C-19 acids. These results indicated that the presence of a 7β-acetoxy group does not inhibit the fungal oxidation of C-19 in 7β-acetoxy-ent-kaur-16-ene, but avoids the ring B contraction that leads to the gibberellins and the 6β-hydroxylation necessary for the formation of seco-ring B ent-kaurenoids. The biotransformation of 7β-acetoxy-ent-trachylobane (trachinol acetate) (27) only led to the formation of 7β-acetoxy-18-hydroxy-ent-trachylobane (33). 相似文献
7.
Braulio M. Fraga Antonio G. Gonzalez James R. Hanson Melchior G. Hernandez 《Phytochemistry》1981,20(1):57-61
The preparation of ent-3β-hydroxykaur-16-ene from linearol and of ent -3β,18-dihydroxykaur-16-ene from foliol is described. The microbiological transformation of these and of foliol by Gibberella fujikuroi has been studied. A 3α-hydroxyl group appears to exert an inhibitory effect on transformations involving oxidation at C-19. 相似文献
8.
Kenji Mori 《Bioscience, biotechnology, and biochemistry》2013,77(12):2899-2905
3-Isobutyroxy-β-ionone (III) is the proposed structure of quiesone, the naturally occurring inhibitor of the germination of Peronospora tabacina conidia. This was synthesized as a racemate and shown to possess qualitatively identical biological activity as quiesone itself. Employing an intermediate of this synthesis, dl-dehydrovomifoliol (VII) was also synthesized. 相似文献
9.
Vladimír Křen Alois Pískala Petr Sedmera Vladimír Havlíěek Věra Přikrylová Myriam Witvrouw 《Nucleosides, nucleotides & nucleic acids》2013,32(1-2):97-106
Abstract N-β-D-Ribosides of agroclavine (1), elymoclavine (2), lysergene (4), lysergol (3), and 9, 10-dihydrolysergol (5) were prepared by SnCl4 catalyzed ribosylation of their TMS derivatives with 1-O-acetyl-2, 3,5-tri-O-benzoyl-β-D-ribofuranose. None of the new compounds exhibited activity against HIV or other viruses tested. 相似文献
10.
α- and γ-l-Glutamyl dipeptides of l-β-phenyl-β-alanine are synthesized for the first time from l-glutamic acid and l-β-phenyl-β-alanine. In addition, the preparations and the properties of new intermediates, that is, l-β-phenyl-β-alanine benzylester p-toluenesulfonate and the N-carbobenzyloxy-α- and γ-dipeptide benzylesters, are described. Further proof of the structure previously proposed for the naturally occurring peptide is obtained by a critical comparison of the isolated and synthetic materials by various physical and chemical methods. 相似文献
11.
Horinouchi N Ogawa J Kawano T Sakai T Saito K Matsumoto S Sasaki M Mikami Y Shimizu S 《Biotechnology letters》2006,28(12):877-881
A one-pot enzymatic synthesis of 2′-deoxyribonucleoside from glucose, acetaldehyde, and a nucleobase was established. Glycolysis by baker’s yeast (Saccharomyces cerevisiae) generated ATP which was used to produce d-glyceraldehyde 3-phosphate production from glucose via fructose 1,6-diphosphate. The d-glyceraldehyde 3-phosphate produced was transformed to 2′-deoxyribonucleoside via 2-deoxyribose 5-phosphate and then 2-deoxyribose 1-phosphate in the presence of acetaldehyde and a nucleobase by deoxyriboaldolase, phosphopentomutase expressed in Escherichia coli, and a commercial nucleoside phosphorylase. About 33 mM 2′-deoxyinosine was produced from 600 mM glucose, 333 mM acetaldehyde and 100 mM adenine in 24 h. 2′-Deoxyinosine was produced from adenine due to the adenosine deaminase activity of E. coli transformants. 相似文献
12.
Christophe Ricco Gilbert Revial Clotilde Ferroud Olivier Hennebert Robert Morfin 《Steroids》2011,76(1-2):28-30
The synthesis of 7β-hydroxy-epiandrosterone (6) possessing strong anti-inflammatory properties was achieved starting from 3β-acetoxy-17,17-(ethylenedioxy)-5-androsten (1). This approach involved as a main step an allylic oxidation of the C-7 followed by two reduction reactions of the double bond and of the carbonyl group. This stereoselective synthesis in 5 steps gave 7β-hydroxy-epiandrosterone in 63% overall yield. 相似文献
13.
Takashi Utagawa Hirokazu Morisawa Shigeru Yamanaka Akihiro Yamazaki Yoshio Hirose 《Bioscience, biotechnology, and biochemistry》2013,77(9):2711-2717
The microbial synthesis of some purine 2′-amino-2′-deoxyribonucleosides from purine bases and 2′-amino-2′-deoxyuridine is described. Various bacteria, especially Erwinia herbicola, Salmonella schottmuelleri, Enterobacter aerogenes and Escherichia coli, were able to transfer the aminoribosyl moiety of 2′-amino-2′-deoxyuridine to purine bases (transaminoribosylation) in the presence of inorganic phosphate. The optimum conditions for the reaction were pH 7.0 and 63°C. No reaction was observed in the absence of inorganic phosphate and the optimum concentration of it was around 30 mm. Adenine, guanine, 2-chlorohypoxanthine and hypoxanthine were transformed to the corresponding 2′-amino-2′-deoxyribonucleosides by the catalytic activity of the wet cell paste of Enterobacter aerogenes AJ 11125. The enzymatically synthesized purine 2′-amino-2′-deoxyribonucleosides were isolated and identified by physicochemical means. 2′-Amino-2′-deoxyadenosine strongly inhibited the growth of Hela cells in tissue culture, and the ED50 was 2.5μ/ml. 相似文献
14.
Spectrophotometric Methods for Monitoring the Microbial Transformation of Steroids: I. Determination of 9α-Fluorohydrocortisone and 9α-Fluoro-16α-Hydroxyhydrocortisone in Fermentation Broths
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Eugene Ivashkiv 《Applied microbiology》1970,20(2):251-253
A method has been devised for the determination of 9alpha-fluorohydrocortisone and 9alpha-fluoro-16alpha-hydroxyhydrocortisone in fermentation broths. The method involves extraction of the two steroids from the broth with ethyl acetate, separation through the formation of the water-soluble borate complex of the vicinally hydroxylated steroid, and estimation of each steroid spectrophotometrically. 相似文献
15.
Early studies led to the identification of 11β-aryl-4',5'-dihydrospiro[estra-4,9-diene-17β,4'-oxazole] analogs with potent and more selective antiprogestational activity compared to antiglucocorticoid activity than mifepristone. In the present study, we replaced the 4'-dimethylaminophenyl group of mifepristone with the benzoxazol group to give 5a-d. We also prepared the 17β-formamido analogs 6a,b using a new synthetic strategy via the intermediate epoxide 21. These compounds were evaluated for their antagonist hormonal properties using the T47D cell-based alkaline phosphatase assay and the A549 cell-based functional assay. Compound 5c showed potent antagonist activity at GR with better selectivity for GR versus PR than mifepristone and is a promising lead for further development. 相似文献
16.
Braulio M. Fraga Pedro Gonzalez Victoria Gonzalez-Vallejo Ricardo Guillermo Luz N. Diaz 《Phytochemistry》2010,71(11-12):1313-1321
The microbiological transformation of 7α,19-dihydroxy-ent-atis-16-ene by the fungus Gibberella fujikuroi gave 19-hydroxy-7-oxo-ent-atis-16-ene, 13(R),19-dihydroxy-7-oxo-ent-atis-16-ene, 7α,11β,19-trihydroxy-ent-atis-16-ene and 7α,16β,19-trihydroxy-ent-atis-16-ene, while the incubation of 19-hydroxy-7-oxo-ent-atis-16-ene afforded 13(R),19-dihydroxy-7-oxo-ent-atis-16-ene and 16β,17-dihydroxy-7-oxo-ent-atisan-19-al. The biotransformation of 7-oxo-ent-atis-16-en-19-oic acid gave 6β-hydroxy-7-oxo-ent-atis-16-en-19-oic acid, 6β,16β,17-trihydroxy-7-oxo-19-nor-ent-atis-4(18)-ene and 3β,7α-dihydroxy-6-oxo-ent-atis-16-en-19-oic acid. 相似文献
17.
《Journal of steroid biochemistry》1983,18(1):81-87
The α- and β-anomers of the 17β-d-glucuronide conjugate of ethynylestradiol were synthesized by the SnCl4-promoted reaction between β-acetoxy GAM and the t-17β-hydroxyl group of EE2-3-acetate. The conjugates were resolved by crystallization and HPLC. Positive identification was established by u.v. spectrophotometry, i.r. and mass spectrometry and 1H- and 134C-n.m.r. The structure of the β-anomer was confirmed by X-ray crystallographic analysis. In addition, the α-anomer was refractory to hydrolysis by bovine β-glucuronidase, establishing a biochemical difference between the conjugate pair. 相似文献
18.
A. H. Moustafa H. A. Morsy M. G. Assy A. Z. Haikal 《Nucleosides, nucleotides & nucleic acids》2013,32(9):835-845
5-Acetyl-2-aryl-6-methyl-4-(2,3,4,6-tetra- O -acetyl-β-D-glucopyranosylmercapto)pyramidines 3a–c were obtained by the reaction of 5-acetyl-2-aryl-6-methyl-pyrimidine thiol 1a–c with 2,3,4,6-tetra- O -acetyl-α-D-glucopyranosyl bromide (2) in aq. KOH/acetone. The reaction of 1a–c with peracetylated galactose 5 and peracetylated ribose 8 under MW irradiation gave 5-acetyl-2-aryl-6-methyl-4-(2,3,4,6-tetra- O -acetyl-β-D-galactopyranosylmercapto)pyrimidine 6a–c and 5-acetyl-2-aryl-6-methyl-4-(2,3,5-tri- O -acetyl-β-D-ribofuranosylmercapto)pyrimidines 9a–c. The deprotection of 3a–c, 6a–c, and 9a–c in the presence of methanol and TEA/H2O yielded the deprotected products 4a–c, 7a–c, and 10a–c. The structures of the compounds were confirmed by using IR, 1H, 13C spectra and microanalysis. Selected members of these compounds were screened for antimicrobial activity. 相似文献
19.
HMBPP ((E)-4-hydroxy-3-methyl-2-butenyl pyrophosphate) is a highly potent innate immunogen that stimulates human γδ T cells expressing the Vγ2Vδ2 T cell antigen receptor. To determine if glycoside conjugates of HMBPP retain activity, the 4-β-glucoside and its acetylated homolog were synthesized and tested for their ability to stimulate γδ T cells. The glycoside HMBPP conjugate stimulated human γδ T cells with an EC(50) of 78nM. The tetraacetyl glycoside HMBPP conjugate was also active (EC(50)=360nM). The two isomeric mono-β-glucosides of the parent (E)-2-methylbut-2-ene-1,4-diol, however, were not active. Thus, HMBPP glycosylated at the 4-OH position stimulates γδ T cells as long as the pyrophosphate moiety is present. 相似文献
20.
A. E. Zemlyakov V. N. Tsikalova L. R. Azizova V. Ya. Chirva E. L. Mulik M. V. Shkalev O. V. Kalyuzhin M. V. Kiselevsky 《Russian Journal of Bioorganic Chemistry》2008,34(2):223-229
Phenyl, p-tolyl, and p-tert-butylphenyl β-1-thio-N-acetylglucosaminides were synthesized by the treatment of thiophenols with peracetate of α-D-glucosaminyl chloride in the presence of triethylamine or under the conditions of phase-transfer catalysis with quaternary
ammonium salts. The compounds synthesized were used for obtaining of glycosides of 4,6-O-isopropylidene-N-acetylmuramic acid, which were coupled with L-Ala-D-Glu(NH2)-OBzl and then deprotected to obtain the target aryl β-thioglycosides of N-acetylmuramyl-L-analyl-D-isoglutamine (MDP). The aryl β-thioglycosides of MDP were found to stimulate an antibacterial resistance toward Staphylococcus aureus in mice. The reliable induction of the spontaneous activity of natural killers in the population of blood mononuclear cells
was observed only for phenyl β-thio-MDP at a dose of 200 μg/ml.
Original Russian Text ? A.E. Zemlyakov, V.N. Tsikalova, L.R. Azizova, V.Ya. Chirva, E.L. Mulik, M.V. Shkalev, O.V. Kalyuzhin,
M.V. Kiselevsky, 2008, published in Bioorganicheskaya Khimiya, 2008, Vol. 34, No. 2, pp. 245–251. 相似文献