- Syntheses of hydantocidin and C-2-thioxohydantocidin
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Hydantocidin (12), a naturally occurring strong herbicide, was synthesized in 35.2% overall yield, with accompanying 5-epi-hydantocidin (12′) in 9.6% overall yield via isothiocyanate (13) and spiro-hydantoin (10) from 2,3-O-isopropylidene-D-ribono-1,4-lactone (1). C-2-Thioxo-hydantocidin (24) was also synthesized in 16.5% overall yield with accompanying 5-epi-C-2-thioxohydantocidin (24′, 9.2% yield) via isothiocyanate (22).
- Shiozaki, Masao
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p. 2077 - 2088
(2007/10/03)
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- Synthesis of hydantocidin and C-2-thioxo-hydantocidin
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Hydantocidin, a naturally occurring strong herbicide, was synthesized in an overall yield of 35.2%, with the accompanying 1′-epi-hydantocidin in overall 9.6% yield from 2,3-O-isopropylidene-D-ribono-1,4-lactone. C-2-thioxo-hydantocidin and its spiro-epimer were also synthesized in an overall yield of 14.4% and 8.5%, respectively.
- Shiozaki, Masao
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p. 147 - 150
(2007/10/03)
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- Natural Products as Pesticides: Two Examples of Stereoselective Synthesis
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The strategy and synthetic efforts leading to efficient stereoselective syntheses of thiangazole, a tris-thiazolinyl-oxazole metabolite isolated from Polyangium spp., and hydantocidin, a spironucleoside metabolite isolated from Streptomyces hygroscopicus, are discussed.
- Frueh, Thomas,Chemla, Philippe,Ehrler, Juerg,Farooq, Saleem
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- Novel synthesis of (+)-hydantocidin based on the plausible biosynthetic pathway
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The title synthesis was examined by employing two synthetic schemes which feature N,O-spiroketal formation as a key step. Although the stepwise synthesis starting with D-fructose and proceeding through the D-psicose derivatives successfully produced a mixture of (+)-hydantocidin (1) and its C5-epimer [(-)-5-epihydantocidin (2)], the one-step synthesis utilizing D-isoascorbic acid and urea as starting materials was found to give 2 more selectively than 1. Studies on the key N,O-spiroketal formation and epimerization between 1 and 2 were also carried out to explore some novel aspects of the obtained results.
- Nakajima, Noriyuki,Matsumoto, Miyoko,Kirihara, Masayuki,Hashimoto, Masaru,Katoh, Tadashi,Terashima, Shiro
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p. 1177 - 1194
(2007/10/03)
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- One-step synthesis of (-)-5-epi-hydantocidin
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One-step synthesis of (-)-5-epi-hydantocidin was achieved by heating a mixture of D-isoascorbic acid and urea without solvent. Studies on N,O-spiroketal formation and epimerization between (+)-hydantocidin and (-)-5-epi-hydantocidin were also carried out to explore some mechanistic aspects of the obtained results.
- Nakajima, Noriyuki,Kirihara, Masayuki,Matsumoto, Miyoko,Hashimoto, Masaru,Katoh, Tadashi,Terashima, Shiro
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p. 503 - 508
(2007/10/03)
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- PSICOFURANOSE AND PSICOPYRANOSE DERIVATIVES
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D-psicofuranose and D-psicopyranose derivatives represented by general formulae (I) and (II), useful as the key intermediates in a novel process for producing hydantocidin; wherein R1 through R8 may be the same or different from one another and each represents hydrogen or a hydroxyl-protecting group; and X represents optionally protected hydroxymethyl, carboxyl, carbamoyl or allophanoyl.
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- Synthesis of 5-epiHydantocidin from D-Ribose
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Tetra-n-propyl ammonium perruthenate in the presence of morpholin-N-oxide induced the unanticipated transformation of the epimeric α-azido-1,4-lactones 4 into the bicyclic amine 3 and provided the key step in the synthesis of 5-epihydantocidin 2.Brief investigations into the acid catalysed equilibration of hydantocidin 1 and 5-epihydantocidin 2 are described.
- Fairbanks, Antony J.,Fleet, George W. J.
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p. 3881 - 3894
(2007/10/02)
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- Stereoselective bromination of β-ribofuranosyl amide. Enantioselective synthesis of (+)-hydantocidin
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The synthesis of hydantocidin, a potent herbicidal natural product, is highlighted by a stereoselective bromination of β-D-ribofuranosyl amide to give only the α-bromo β-amide and subsequent spirocyclization about the anomeric position with silver cyanate to form the hydantoin moiety.
- Harrington,Harrington, Philip M.,Jung,Jung, Michael E.
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p. 5145 - 5148
(2007/10/02)
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- Stereoselectivity synthesis of (+)-hydantocidin
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The naturally occurring spironuceleoside (+)-hydantocidin 1 was synthesized from 1,2:3,4-di-O-isopropylidene-D-psicofuranose using a new oxygen-bridged intramolecular Vorbruggen coupling of the N-hydroxyurea 5 in presence of a catalytic amount of trimethylsilytriflate.
- Chemla
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p. 7391 - 7394
(2007/10/02)
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- A novel biogenetic type synthesis of (+)-hydantocidin
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The title synthesis was accomplished by featuring the proposed biosynthetic pathway. The synthesis commenced with the D-psicose derivative readily obtainable from D-fructose and employed intramolecular N, O-spiroketal formation of the open-chain N-acylurea derivative as a key step.
- Matsumoto, Miyoko,Kirihara, Masayuki,Yoshino, Toshiharu,Katoh, Tadashi,Terashima, Shiro
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p. 6289 - 6292
(2007/10/02)
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- Synthetic studies on (+)-hydantocidin (1): A total synthesis of (+)-hydantocidin, a new herbicidal metabolite from microorganism
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A total synthesis of (+)-hydantocidin 1, a new class of ribofuranose derivative exhibiting herbicidal activity, is reported. The spiro-hydantoin ring at the anomeric position of D-ribofuranose was constructed from substituted hydantoin derivatives 6, 7, and 12 through acid and base-promoted cyclization methods.
- Mio, Shigeru,Ichinose, Reiji,Goto, Kuniko,Sugai, Soji,Sato, Sadao
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p. 2111 - 2120
(2007/10/02)
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- Synthetic studies on (+)-hydantocidin (3): A new synthetic method for construction of the spiro-hydantoin ring at the anomeric position of D-ribofuranose
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A facile synthetic route for the large-scale preparation of a herbicidal natural product, (+)-hydantocidin is described. The protected D-psicose 6, prepared in five steps from D-fructose, was stereospecifically converted to azido-amide 14 by N-glycosidation (TMSN3/TMSOTf), oxidation and animation. Hydantoin ring-construction on 14 was achieved by aza-Wittig reaction (PBu3/CO2/CH3CN) to give 16 without epimerization at the anomeric center. After acetylation, stepwise deprotection of 24 afforded (+)-hydantocidin 1 in 16% overall yield from D-fructose.
- Mio, Shigeru,Kumagawa, Yuko,Sugai, Soji
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p. 2133 - 2144
(2007/10/02)
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