- Enantiospecific synthesis of (-)-5-epi-shikimic acid and (-)-shikimic acid
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Diastereoselective reaction of 2,3-O-isopropylidene-D-ribose with allylmagnesium chloride gave a 5 : 1 mixture of triols 4 and 5, which were then converted to nitrones 8 and 9. Intramolecular nitrone cycloaddition gave the isoxazolidines 10 and 11, which on acetylation gave the corresponding acetates 12 and 13 which were separated by repeated crystallisation. The major adduct 12 was converted to (-)-5-epi-shikimic acid 2. Reaction of the ribonolactone derivative 20 with allylmagnesium chloride gave the hemiacetal 21. Reduction of compound 21 with DIBAL afforded exclusively the diol 22, which was desilylated to give the triol 5. Similar chemistry to that employed for the synthesis of (-)-5-epi-shikimic acid 2 with the diol 5 resulted in the synthesis of (-)-shikimic acid 1.
- Jiang, Shende,McCullough, Kevin J.,Mekki, Boualem,Singh, Gurdial,Wightman, Richard H.
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- Chemical and toxicological studies on bracken fern, Pteridium aquilinum var. latiusculum. VI. Isolation of 5-O-caffeoylshikimic acid as an antithiamine factor
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5-O-Caffeoylshikimic acid (dactylifric acid) was isolated from bracken fern as a major constituent of its acutely toxic fraction, which causes depression of leucocytes and thrombocytes in calves. 5-O-Caffeoylshikimic acid exhibited an antithiamine effect in vitro, but had no hematuric effect in guinea pigs.
- Fukuoka
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- Hydroaromatic equilibration during biosynthesis of shikimic acid
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The expense and limited availability of shikimic acid isolated from plants has impeded utilization of this hydroaromatic as a synthetic starting material. Although recombinant Escherichia coli catalysts have been constructed that synthesize shikimic acid from glucose, the yield, titer, and purity of shikimic acid are reduced by the sizable concentrations of quinic acid and 3-dehydroshikimic acid that are formed as byproducts. The 28.0 g/L of shikimic acid synthesized in 14% yield by E. coli SP1.1/pKD12.138 in 48 h as a 1.6:1.0:0.65 (mol/mol/mol) shikimate/quinate/dehydroshikimate mixture is typical of synthesized product mixtures. Quinic acid formation results from the reduction of 3-dehydroquinic acid catalyzed by aroE-encoded shikimate dehydrogenase. Is quinic acid derived from reduction of 3-dehydroquinic acid prior to synthesis of shikimic acid? Alternatively, does quinic acid result from a microbe-catalyzed equilibration involving transport of initially synthesized shikimic acid back into the cytoplasm and operation of the common pathway of aromatic amino acid biosynthesis in the reverse of its normal biosynthetic direction? E. coli SP1.1/pSC5.214A, a construct incapable of de novo synthesis of shikimic acid, catalyzed the conversion of shikimic acid added to its culture medium into a 1.1:1.0:0.70 molar ratio of shikimate/quinate/dehydroshikimate within 36 h. Further mechanistic insights were afforded by elaborating the relationship between transport of shikimic acid and formation of quinic acid. These experiments indicate that formation of quinic acid during biosynthesis of shikimic acid results from a microbe-catalyzed equilibration of initially synthesized shikimic acid. By apparently repressing shikimate transport, the aforementioned E. coli SP1.1/pKD12.138 synthesized 52 g/L of shikimic acid in 18% yield from glucose as a 14:1.0:3.0 shikimate/quinate/dehydroshikimate mixture.
- Knop,Draths,Chandran,Barker,Von Daeniken,Weber,Frost
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- Synthesis of aminoshikimic acid
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5-Amino-5-deoxyshikimic acid (aminoshikimic acid) was synthesized from glucose using recombinant Amycolatopsis mediterranei and also synthesized by a tandem, two-microbe route employing Bacillus pumilus and recombinant Escherichia coli.
- Guo, Jiantao,Frost
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- An enantioconvergent route to (-)-shikimic acid via a palladium-mediated elimination reaction
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(Matrix presented) (-)-Shikimic acid, the key intermediate in the shikimate pathway in plants and microorganisms, has been synthesized in an enantioconvergent manner from both enantiomeric starting materials by employing a palladium-mediated elimination reaction as the key step.
- Yoshida, Naoyuki,Ogasawara, Kunio
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- Enantiospecific synthesis of (-)-5-epi-shikimic acid and a new route to (-)-shikimic acid
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(-)-Shikimic acid (1) and (-)-5-epi-shikimic acid (2) have each been prepared enantiospecifically and with high diastereoselectivity from D-ribose.
- Jiang, Shende,Mekki, Boualem,Singh, Gurdial,Wightman, Richard H.
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- New phenolic compounds from Meehania urticifolia
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A new phenylethanoid glycoside, rashomoside A (1), a new phenolic glucoside, rashomoside B (2), and a new shikimic acid derivative (3) were isolated from Meehania urticifolia together with 12 known flavones (4-15), three known phenylethanoid glycosides (16-18), and 13 other compounds (19-31). The structure of each of these compounds was elucidated based on the results of spectroscopic analysis.
- Murata, Toshihiro,Miyase, Toshio,Yoshizaki, Fumihiko
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- Stereodivergent Syntheses of All Stereoisomers of (?)-Shikimic Acid: Development of a Chiral Pool for the Diverse Polyhydroxy-cyclohexenoid (or -cyclohexanoid) Bioactive Molecules
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Novel stereodivergent total syntheses of all the seven stereoisomers of (?)-shikimic acid [(?)-SA 1] have been systematically performed. (+)-ent-SA ent-1 was synthesized from (?)-SA 1 via 9 steps in 31 % overall yield; (?)-3-epi-SA 2 was synthesized from (?)-SA 1 via 5 steps in 66 % overall yield; (+)-3-epi-ent-SA ent-2 was synthesized from (?)-SA 1 via 7 steps in 43 % overall yield; (?)-4-epi-SA 3 was synthesized from (?)-SA 1 via 11 steps in 32 % overall yield; (+)-4-epi-ent-SA ent-3 was synthesized from (?)-SA 1 via 7 steps in 42 % overall yield; (?)-5-epi-SA 4 was synthesized from (?)-SA 1 via 6 steps in 56 % overall yield; and (+)-5-epi-ent-SA ent-4 was synthesized from (?)-SA 1 via 12 steps in 29 % overall yield. The stereochemistry of all the above seven stereoisomers of (?)-SA 1 were further studied by two dimensional (2D) 1H NMR technique.
- He, Yun-Gang,Huang, Yong-Kang,Xu, Zhang-Li,Xie, Wen-Jing,Luo, Yong-Qiang,Li, Feng-Lei,Zhu, Xing-Liang,Shi, Xiao-Xin
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p. 4318 - 4332
(2021/07/21)
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- A C 2-symmetric chiral pool-based flexible strategy: Synthesis of (+)- and (-)-shikimic acids, (+)- and (-)-4- epi -shikimic acids, and (+)- and (-)-pinitol
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Via combination of a novel acid-promoted rearrangement of acetal functionality with the controlled installation of the epoxide unit to create the pivotal epoxide intermediates in enantiomerically pure form, a simple, concise, flexible, and readily scalable enantiodivergent synthesis of (+)- and (-)-shikimic acids and (+)- and (-)-4-epi-shikimic acids has emerged. This simple strategy not only provides an efficient approach to shikimic acids but also can readily be adopted for the synthesis of (+)- and (-)-pinitols. These concise total syntheses exemplify the use of pivotal allylic epoxide 14 and its enantiomer ent-14. A readily available inexpensive C2-symmetric l-tartaric acid (7) served as key precursor. In general, the strategy here provides a neat example of the use of a four-carbon chiron and offers a good account of the synthesis of functionalized cyclohexane targets.
- Ananthan, Bakthavachalam,Chang, Wan-Chun,Lin, Jhe-Sain,Li, Pin-Hui,Yan, Tu-Hsin
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p. 2898 - 2905
(2014/05/06)
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- A concise route to (-)-shikimic acid and (-)-5-epi-shikimic acid, and their enantiomers via Barbier reaction and ring-closing metathesis
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A simple route for the synthesis of naturally occurring (-)-shikimic acid, (-)-5-epi-shikimic acid, and their enantiomers from d-ribose-derived enantiomeric aldehydes 8a and 8b by employing Barbier reaction and ring-closing metathesis as key steps has bee
- Kancharla, Pavan K.,Doddi, Venkata Ramana,Kokatla, Hariprasad,Vankar, Yashwant D.
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scheme or table
p. 6951 - 6954
(2010/02/28)
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- Medicinal flowers. XXX. Eight new glycosides, everlastosides F - M, from the flowers of Helichrysum arenarium
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Eight new glycosides, everlastosides F (1), G (2), H (3), I (4), J (5), K (6), L (7), and M (8), were isolated from the methanolic extract of the flowers of Helichrysum arenarium. Their structures were elucidated on the basis of chemical and physicochemic
- Morikawa, Toshio,Wang, Li-Bo,Ninomiya, Kiyofumi,Nakamura, Seikou,Matsuda, Hisashi,Muraoka, Osamu,Wu, Li-Jun,Yoshikawa, Masayuki
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experimental part
p. 853 - 859
(2010/03/26)
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- High shikimate production from quinate with two enzymatic systems of acetic acid bacteria
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3-Dehydroshikimate was formed with a yield of 57-77% from quinate via 3-dehydroquinate by two successive enzyme reactions, quinoprotein quinate dehydrogenase (QDH) and 3-dehydroquinate dehydratase, in the cytoplasmic membranes of acetic acid bacteria. 3-Dehydroshikimate was then reduced to shikimate (SKA) with NADP-dependent SKA dehydrogenase (SKDH) from the same organism. When SKDH was coupled with NADP-dependent D-glucose dehydrogenase (GDH) in the presence of excess D-glucose as an NADPH regenerating system, SKDH continued to produce SKA until 3-dehydroshikimate added initially in the reaction mixture was completely converted to SKA. Based on the data presented, a strategy for high SKA production was proposed.
- Adachi, Osao,Ano, Yoshitaka,Toyama, Hirohide,Matsushita, Kazunobu
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p. 2579 - 2582
(2008/02/12)
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- Arene cis-dihydrodiols-useful precursors for the preparation of antimetabolites of the shikimic acid pathway: application to the synthesis of 6,6-difluoroshikimic acid and (6S)-6-fluoroshikimic acid
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The synthesis of 6,6-difluoroshikimic acid (11) has been achieved in ten steps from the enantiopure diol 16, which is derived from enzymatic cis-dihydroxylation of iodobenzene. The versatility of the synthetic strategy has been demonstrated by the preparation of the known antimicrobial agent, (6S)-6-fluoroshikimic acid (5).
- Humphreys, Jane L.,Lowes, David J.,Wesson, Karen A.,Whitehead, Roger C.
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p. 5099 - 5108
(2007/10/03)
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- Creation of a shikimate pathway variant
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The competition between the Escherichia coli carbohydrate phosphotransferase system and 3-deoxy-d-arabino-heptulosonate 7-phosphate (DAHP) synthase for phosphoenolpyruvate limits the concentration and yield of natural products microbially synthesized via the shikimate pathway. To circumvent this competition for phosphoenolpyruvate, a shikimate pathway variant has been created. 2-Keto-3-deoxy-6-phosphogalactonate (KDPGal) aldolases encoded by Escherichia coli dgoA and Klebsiella pneumoniae dgoA are subjected to directed evolution. The evolved KDPGal aldolase isozymes exhibit 4-8-fold higher specific activities relative to that for native KDPGal aldolase with respect to catalyzing the condensation of pyruvate and d-erythrose 4-phosphate to produce DAHP. To probe the ability of the created shikimate pathway variant to support microbial growth and metabolism, growth rates and synthesis of 3-dehydroshikimate are examined for E. coli constructs that lack phosphoenolpruvate-based DAHP synthase activity and rely on evolved KDPGal aldolase for biosynthesis of shikimate pathway intermediates and products. Copyright
- Ran, Ningqing,Draths,Frost
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p. 6856 - 6857
(2007/10/03)
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- Nonenzymatic breakdown of the tetrahedral (α-carboxyketal phosphate) intermediates of MurA and AroA, two carboxyvinyl transferases. Protonation of different functional groups controls the rate and fate of breakdown
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The mechanisms of nonenzymatic breakdown of the tetrahedral intermediates (THIs) of the carboxyvinyl transferases MurA and AroA were examined in order to illuminate the interplay between the inherent reactivities of the THIs and the enzymatic strategies used to promote catalysis. THI degradation was through phosphate departure, with C-O bond cleavage. It was acid catalyzed and dependent on the protonation state of the carboxyl of the α-carboxyketal phosphate functionality, with ionizations at pKa = 3.2 ± 0.1 and 4.3 ± 0.1 for MurA and AroA THIs, respectively. The solvent deuterium kinetic isotope effect for MurA THI at pL 2.0 was 1.3 ± 0.4, consistent with general acid catalysis. The pKa's suggested intramolecular general acid catalysis through protonation of the bridging oxygen of the phosphate, though H3O+ catalysis was also possible. The product distribution varied with pH. The dominant breakdown products were {pyruvate + phosphate + R-OH} (R-OH = UDP-GlcNAc or shikimate 3-phosphate) at all pH's, particularly low pH. At higher pH's, increasing proportions of ketal, arising from intramolecular substitution of phosphate by the adjacent hydroxyl and the enolpyruvyl products of phosphate elimination were observed. With MurA THI, the product distribution fitted to pK a's 1.6 and 6.2, corresponding to the expected pKa's of a phosphate monoester. C-O bond cleavage was demonstrated by the lack of monomethyl [33P]phosphate formed upon degrading MurA [ 33P]THI in 50% methanol. General acid catalysis through the bridging oxygen is consistent with the location of the previously proposed general acid catalyst for THI breakdown in AroA, Lys22.
- Byczynski, Bartosz,Mizyed, Shehadeh,Berti, Paul J.
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p. 12541 - 12550
(2007/10/03)
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- Benzene-free synthesis of phenol
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Heating shikimic acid in near-critical water leads to the formation of phenol. Since shikimic acid can now be obtained by the microbial conversion of glucose, a benzene-freer route to phenol could become an alternative to the industrial Hock oxidation of cumene derived from benzene (see scheme).
- Gibson, James M.,Thomas, Phillip S.,Thomas, Joshua D.,Barker, Jessica L.,Chandran, Sunil S.,Harrup, Mason K.,Draths, Karen M.,Frost, John W.
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p. 1945 - 1948
(2007/10/03)
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- Direct conversion of 1,2-diol into allyl sulfide. Regioselective transformation of (-)-quinic acid to (-)-shikimic acid
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Exo-1,2-diols 3 and 4 were efficiently converted into the corresponding allyl sulfides by means of tri-n-butylphosphine (Bu3P) and diphenyl disulfide (PhS)2. This method was applied to the introduction of a carbon- carbon double bond from diol 11 to give allyl sulfide 12 in a highly regioselective manner. The allyl sulfide 12 was transformed into (-)-shikimic acid (1) in four steps.
- Shinada, Tetsuro,Yoshida, Yasutaka,Ohfune, Yasufumi
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p. 6027 - 6028
(2007/10/03)
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- A concise enantio- and diastereo-controlled synthesis of (-)-quinic acid and (-)-shikimic acid
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(-)-Quinic acid and (-)-shikimic acid, both recognized as the key intermediates in the shikimate pathway in plants and microorganisms, have been synthesized concisely in an enantio- and diastereo-controlled manner starting from a synthetic equivalent of (R)-4-hydroxycyclohex-2-enone.
- Hiroya, Kou,Ogasawara, Kunio
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p. 2033 - 2034
(2007/10/03)
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- A new stereocontrolled route to (-)-shikimic acid
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A new stereocontrolled route to (-)-shikimic acid, the component of the fruit of shikimi tree, Illicium religiosum, and the key biogenetic precursor of a variety of aromatic natural products, has been developed using the chiral 2,5-cyclohexadienol synthon.
- Kamikubo, Takashi,Ogasawara, Kunio
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p. 987 - 988
(2007/10/03)
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- SPECIFITY OF E. COLI SHIKIMATE DEHYDROGENASE TOWARDS ANALOGUES OF 3-DEHYDROSHIKIMIC ACID
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Analogues of 3-dehydroshikimic acid which lack the C-4 and C-5 hydroxyl groups have been synthesised and assayed as substrates for shikimate dehydrogenase.The presence of the C-4 hydroxyl group is found to be very important for specificity, whereas the C-5 hydroxyl group is not.The enzyme exhibits enantioselectivity at C-1 and C-4 of the racemic substrate analogues.
- Bugg, Timothy D. H.,Abell, Chris,Coggins, John R.
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p. 6779 - 6782
(2007/10/02)
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- Total Synthesis of (-)-Chorismic Acid and (-)-Shikimic Acid
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A survey of the enantioselective hydrolyses of 5a-h and 6a-c with commercially available lipases and cholesterol esterases is reported.A procedure for the preparative-scale synthesis of enantiomerically pure (+)-4 and (-)-4 by the enantioselective hydrolysis of 6a or 6b with cholesterol esterase from bovine pancreas is described.Enantiomerically pure (-)-3 is prepared from either (+)-4 or (-)-4.A short total synthesis of (-)-chorismic acid (22percent) from (-)-3 and of (-)-shikimic acid (94percent) from (-)-4 is reported.
- Pawlak, John L.,Berchtold, Glenn A.
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p. 1765 - 1771
(2007/10/02)
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- Tannins and Related Compounds. XXV. A New Class of Gallotannins Possessing a (-)-Shikimic Acid Core from Castanopsis cuspidata var. sieboldii Nakai. (1)
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A homologous series of (-)-shikimic acid gallates (I-V) has been isolated, together with 1,6-di-O-galloyl-β-D-glucopyranoside (VI), 5-O-galloyl-D-hamamelose (VII), 2',5-di-O-galloyl-D-hamamelose (VIII) and 2',3,5-tri-O-galloyl-D-hamamelose (IX), from the leaves of Castanopsis cuspidata var. sieboldii Nakai.On the basis of spectroscopic analysis, enzymatic hydrolysis and methanolysis, their structures have been established as 3-O-gallate (I), 3-O-digallate (II), 3-O-trigallate (III), 3,5-di-O-gallate (IV) and 3,4-di-O-gallate (V) of (-)shikimic acid.
- Nonaka, Gen-ichiro,Ageta, Masayuki,Nishioka, Itsuo
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- Enantiospecific Synthesis of Shikimic Acid from D-Mannose: Formation of a Chiral Cyclohexene by Intramolecular Olefination of a Carbohydrate-derived Intermediate
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An enantiospecific synthesis of (-)-shikimic acid from D-mannose in an overall yield of 39percent is described, in which the key step is an intramolecular Wadsworth-Emmons olefination reaction of a phosphonate.Nucleophilic displacement of triflate from benzyl 2,3-O-isopropylidene-5-O-trifluoromethylsulphonyl-α-D-lyxofuranoside by the sodium salt of t-butyl dimethoxyphosphorylacetate provides a rare example of substitution at the C-5 position of a furanose derivative by a carbanion.
- Fleet, George W. J.,Shing, Tony K. M.,Warr, Steven M.
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p. 905 - 908
(2007/10/02)
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- Chemistry of shikimic acid derivatives. Synthesis of specyfically labeled shikimic acid at C-3 or C-4
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Specifically labeled shikimic acids with tritium or deuterium at posiions C-3 or C-4 were synthesized.Commercially available L-shikimic acid was converted to its 3- and 4-ketones, after suitable protection of the hydroxyl groups at C-4, C-5 and C-3, C-5.Reduction of the 3-keto or 4-keto-shikimic acid derivatives with sodium borodeuteride and deprotection gave mostly 3-D-epi-shikimic acid or 4-D-shikimic acid.An internally assisted inversion of the 3-D-epi-shikimic acid derivative and deprotection gave 3-D-shikimic acid.
- Zamir, Lolita O.,Luthe, Corinne
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p. 1169 - 1175
(2007/10/02)
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- SHIKIMIC ACIDS FROM FURAN; METHODS OF STEREOCONTROLLED ACCESS TO 3,4,5-TRIOXIGENATED CYCLOHEXENES
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Oxabicycloheptenes 1 and 2 are converted to 3,4,5-oxigenated cyclohexenes by stereocontrolled hydroxylations and epoxidations coupled with reverse-Michael cleavage of the oxabicyclo system.Three epimers of shikimic acid are synthesized by these methods.
- Rajapaksa, D.,Keay, B. A.,Rodrigo, R.
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p. 826 - 828
(2007/10/02)
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- Asymmetric Diels-Alder Reaction: Applications of Chiral Dienophiles
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The chiral dienophile recently designed and its related compounds react highly diastereoselectively with a wide variety of both achiral and chiral dienes, and the stereochemical outcome of these Diels-Alder reactions is predictable.
- Masamune, Satoru,Reed, Lawrence A.,Davis, Jeffery T.,Choy, William
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p. 4441 - 4444
(2007/10/02)
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- THE SYNTHESIS OF 3- AND 4-DEUTERATED SHIKIMIC ACID
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The synthesis of 3-2H- and 4-2H-L-shikimic acids was accomplished starting from commercially available L-shikimic acid.
- Luthe, Corinne,Zamir, Lolita O.
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p. 4409 - 4412
(2007/10/02)
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- An Entry to Chiral Cyclohexenes from Carbohydrates: A Short, Efficient, and Enantiospecific Synthesis of (-)-Shikimic Acid from D-Mannose
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A short, efficient, and enantiospecific synthesis of (3R,4S,5R)-shikimic acid from benzyl 2,3-O-isopropylidene-α-D-lyxofuranoside (readily available from D-mannose) is described.
- Fleet, George W. J.,Shing, Tony K. M.
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p. 849 - 850
(2007/10/02)
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- 3-Trehalosamine compounds
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Novel antibiotic 3-trehalosamine (U-59,834) producible in a fermentation under controlled conditions using the new microorganism Nocardiopsis trehalosei sp. nov., NRRL 12026. This antibiotic is active against Gram-positive bacteria, for example, Staphylococcus aureus, Bacillus subtilis, and Diplococcus pneumoniae. Thus, 3-trehalosamine can be used in various environments to eradicate or control such bacteria. Antibiotic 3-trehalosamine can be shown by the following structural formula: STR1
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- Antibiotic 354 and process for producing same
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Novel antibiotic 354 (U-54,703) producible in a fermentation under controlled conditions using the new microorganism Streptomyces puniceus subsp. doliceus, NRRL 11160. This antibiotic is active against Gram-negative bacteria, for example, Pseudomonas and Proteus species. Thus, antibiotic 354 can be used in various environments to eradicate or control such bacteria.
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- Composition of matter and process
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Novel antibiotic formulations of antibiotic 354 (U-54,703) and their use in treating susceptible infectious disease in humans and animals.
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- Aminoglycoside antibiotics
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6-0- AND 3'-0-D-glycosyl analogs of 4-0-(α-D-glycosyl)-2-deoxystreptamine, 6-0- and 3'-0-D-glycosyl ortho esters of 4-0-(α-D-glycosyl)-2-deoxystreptamine, novel aminoglycoside antibiotics, and novel intermediates are prepared by a new chemical process. The compounds have utility as antibacterial agents or as intermediates to make antibacterially-active compounds.
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