HETEROCYCLES
An International Journal for Reviews and Communications in Heterocyclic ChemistryWeb Edition ISSN: 1881-0942
Published online by The Japan Institute of Heterocyclic Chemistry
Special Issue
Tetsuji Kametani's Special Issues, Vol. 30, No. 2, 1990
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■ Reactions of a Tetrasubstituted Thiocarbonyl Ylide; New Evidence for Two-Step Cycloadditions
Rolf Huisgen* and Grzegorz Mloston
*Institute of Organic Chemistry, University of Munich, Karlstrasse 23, D-80333, München, Germany
Abstract
Zwitterionic intermediates from aliphatic thiocarbonyl yields and tetrasubstituted acceptor olefins can close the 5-membered ring (thiolane) or the 7-membered ring (ketene imine), undergo rotation, and - shown here - furnish cyclopropane and thione in an intramolecular nucleophilic substitution.
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■ Highly Accelerated Reactions in a Microwave Ovem: Synthesis of Heterocycles
Ajay K. Bose,* Maghar S. Manhas, Malay Ghosh, Vegesna S. Raju, Keiko Tabei, and Zofia Urbancyk-Lipkowska
*Department of Chemistry and Chemical Engineering, Stevens Institute of Technology, Castle Point on the Hudson, Hoboken, NJ 07030, U.S.A.
Abstract
Efficient synthesis of a wide variety of heterocycles on 0.1 to 200 g scale was conducted in organic solvents in a commercial microwave oven in a few minutes at a low energy level. Erlenmeyer flasks were adequate reaction vessels since neither high pressure nor high temperature were involved. Fast monitoring of synthetic reactions was achieved by tlc separation and transfer of tlc spot material directly to a solids probe of a chemical ionization mass spectrometer. Microwave Oven-induced Reaction Enhancement (MORE) chemistry is not due to thermolysis: one reaction was conducted successfully in a reaction vial encased in a block of ice.
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■ Biocatalytic Preparation of Chiral β-Hydroxy Esters Substituted with Heteroring at γ-position
Katsuyuki Kurumaya, Kazuhiko Takatori, Rieko Isii, and Masahiro Kajiwara*
*Department of Medicinal Chemistry, Meiji Pharmaceutical University, 2-522-1 Noshio, Kiyose, Tokyo 204-8588, Japan
Abstract
Asymmetric reduction were examined of β-keto esters substituted with dithiane ring at γ-position with microorganism and gave the alcohol with high optical purity. Also the chiral carbinol with furan ring was obtained by the hydrolysis of the corresponding acetate with lipase or baker’s yeast.
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■ Synthesis of 2-Phenyl-2,3,4,5-tetrshydro-1-benzoxepin-5-ones
Toshio Tatsuoka,* Kayoko Imao, Kenji Suzuki, Makoto Shibata, Fumio Satoh, Seiji Miyano, and Kunihiro Sumoto
*Suntory Institute for Biochemical Research, Suntory Co. Ltd., 1-1-1, Wakayamadai, Shimamotocho, Mishimagun, Osaka 618-0024, Japan
Abstract
A series of 2-phenyl-1-2,3,4,5-tetrahydro-1-benzoxepin-5-ones were synthesized by 2 steps from flavones through 3,4-benzo-5-oxo-2-oxabicyclo[4.1.0]heptanes.
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■ Controlling Factors for the Formation of Pyrrole, Pyridine, and Azepine in Thermal Rearrangement of 2H-Azirines
Masumi Saruwatasi, Kazuaki Isonuma, and Hiroshi Taniguchi*
*Faculty of Engineering, Kyushu University, 6-10-1 Hakozaki, Higashi-ku, Fukuoka 812-8581, Japan
Abstract
Thermal rearrangement of 2-(cyclohexen-1-yl)- and 2-(cyclopenten-1-yl)-2H-azirines, bearing a methyl or a phenyl group at the 2-position of cycloalkenes, was compared with those of corresponding acyclic and benzofuranylazirines. Suppression of the cyclization into pyrrole in favor of pyridine and azepine formations from the azirines having cyclic unsaturation is explained by the strain of fused 2H-pyrrole and the electronic character of vinyl nitrene intermediates.
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■ Structure Determination of a Violet-Blue Flower Flavonoid, Qurcetin 3-Glucosyl(1→2)gentiobioside from Primula polyantha
Norio Saito, Keiko Yoda, Hideyuki Haruyama, Harumitsu Kuwano, and Toshio Honda*
*Faculty of Pharmaceutical Sciences, Hoshi University, 2-4-41 Ebara, Shinagawa-ku, Tokyo 142-8501, Japan
Abstract
The chemical structure of quercetin 3-glucosyl(1→2)gentiobioside, isolated from the violet blue flowers of Primura polyantha was determined to be quercetin 3-O-(β-D-glucopyranosyl(1→2)-O-β-D-glucopyranosyl(1→6))-β-D-glucopyranoside unambiguously based on the spectroscopic data.
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■ Response of 2-Lithio-4,5-dihydrofuran — Ketone Adducts to Acid Catalysis
Leo A. Paquette,* David E. Lawhorn, and Christopher A. Teleha
*Evans Chemical Laboratories, The Ohio State University, 120 W. 18th Avenue, Columbus, Ohio 43210, U.S.A.
Abstract
Tertiary allylic alcohols derived from 1,2-addition of 2-lithio-4,5-dihydrofuran to ketones are shown to be capable of conversion to dimeric spiro-1,4-dioxanes or to monomeric ring-expanded spirocyclic ketones depending upon the conditions of acid catalysis employed.
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■ A Novel Synthesis of Trialkylstannyl- and Silypyridine Derivatives through Diels-Alder Reaction of 6H-1,3-Oxazin-6-ones
Yutaka Yamamoto* and Yasuo Morita
*Faculty of Pharmaceutical Sciences, Tohoku Pharmaceutical University, 4-4-1 Komatsushima, Aoba-ku, Sendai 981-8558, Japan
Abstract
A novel and convenient method for the synthesis of trimethylstannyl- and silylpyridine derivatives through Diels-Alder reaction of 6H-1,3-oxazin-6-ones with trialkylstannyl- and -silylacetylene derivatives was developed.
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■ A Mild and Rapid 1,2-trans-Glycosidation Method via Benzoyl-protected Glycopyranosyl P,P-Diphenyl-N-(p-toluenesulfonyl)phosphinimidates
Shun-ichi Hashimoto, Takeshi Honda, and Shiro Ikegami*
*Faculty of Pharmaceutical Sciences, Teikyo University, 1091-1, Sagamiko, Kanagawa 199-0195, Japan
Abstract
A highly efficient 1,2-trans-glycosidation reaction with a range of acid-labile alcohols has been developed by employing benzoyl-protected glycopyranosyl P,P-diphenyl-N-(p-toluenesulfonyl)phosphinimidates as glycosyl donors.
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■ Reinvestigation of the Reaction of 3-Bromo-4-nitroquinoline 1-Oxide with 1-Morpholinocyclohexene
Yutaka Miura, Yasuo Fujimura, Sakae Takaku, and Masatomo Hamana*
*Chugai Pharmaceutical Company, Ltd., 135, 1-Chome Komakado, Gotemba City, shizuoka 412-8513, Japan
Abstract
Reinvestigation of the reaction of 3-bromo-4-nitroquinoline-1-oxide (2) with 1-morpholinocyclohexene (3) has revealed that the reaction proceeds by a multistep ionic process involving the initial formation of 3-morpholino-4-nitro-2-(2-oxocyclohexyl)quinoline (6) and the subsequent tranformation of 6 into 10-nitro-1,2,3,4-tetrahydrobenzofuro[3,2-b]quinoline (5). Not only 2 reacts with various enamines in the same way, but also 3-bromo-4-nitropyridine N-oxide (7) undergoes the same type of reactions.
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■ Synthwsis of (+)-Galactostatin
Sakae Aoyagi, Satoshi Fujimaki, Naoki Yamazaki, and Chihiro Kibayashi*
*School of Pharmacy, Tokyo University of Pharmacy and Life Science, 1432-1 Horinouchi, Hachioji, Tokyo 192-0392, Japan
Abstract
The chiral synthesis of (+)-galactostatin (3), a new β-galactosidase inhibitor, has been achieved, in which the key step involved a diastereoselective epoxidation of the allylic alcohol (4) derived from L-tartaric acid.
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■ The Nitrogenated Allylic System as an Intramolecular Nucleophile: A New Route to Pyrazoles
Takefumi Momose,* Naoki Toyooka, Takashi Ikuta, and Hironobu Yanagino
*Faculty of Pharmaceutical Sciences, Toyama Medical and Pharmaceutical University, 2630 Sugitani, Toyama, Toyama 930-0194, Japan
Abstract
A new route to pyrazoles via the cyclization of N-allyl-N-nitrosoamides is described.
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■ Lignans and Sesquiterpenoids asa PAF Antagonists
Satoshi Iwakami, Yutaka Ebizuka, and Ushio Sankawa*
*Faculty of Pharmaceutical Sciences, University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan
Abstract
Some lignans and sesquiterpenes were found to have potent PAF antagonist activities. In particular, 6-O-angeloyl- and 6-O-senecioylplenolins (18,19) are the most potent and specific PAF antagonists found in this study.
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■ 2-(Heteroatom-substituted)methyl Penems. IV. Oxygen Derivatives
Marco Alpegiani, Angelo Bedeschi, Franco Giudici, Ettore Perrone, Giuseppina Visentin, Franco Zarini, and Giovanni Franceschi*
*Ricerca&Sviluppo Chimico, Farmitalia Carlo Erba SpA, Via dei Gracchi 35, 20146 Milano, Italy
Abstract
The synthesis of "2-CH2X" penems wherein X is an oxygen atom partof an acyloxy, N-substituted carbamoyloxy, alkoxy or aryloxy residue is described, with emphasis to procedures which exploit a common 2-hydroxymethylpenem precursor. Correlations are attempted between chemical structure of the X moiety and antibacterial activity of obtained compounds.
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■ Synthesis of Oxasteroidal Skeletons by (4+2) Type Cycloaddition of Coumarin and 6-Methyl-2-pyrone with Siloxydienes Mediated by t-Butyldinethylsilyl Triflate
Yong-gyun Lee, Yukinori Utsumi, Katsuo Ohkata, and Kin-ya Akiba*
*Department of Chemistry, Faculty of Science, Hiroshima University, 1-3-1 Kagamiyama, Higashi-Hiroshima, Hiroshima 739-8526, Japan
Abstract
A new simple methodology is described for the preparation of oxasteroidal skeletons containing a lactone ring via cycloaddition of 2-t-butyldimethylsiloxypyrylium triflate (2a,b) with siloxydienes (3).
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■ Versatile Methods of Synthesis of 5 to 8-Membered Ring N-Heterocycles via Intramolectlar Cycloadditons of Allylamines
K. M. Lokanatha Rai and Alfred Hassner*
*Department of Chemistry, Bar-Ilan University, Ramat-Gan 52900, Israel
Abstract
N-Tosylallylamines or homoallylamines were monoalkylated with dibromoalkanes to produce bromoalkylamines 3 or 7. The latter were converted to unsaturated nitro derivatives which, via nitrile oxides, underwent intramolecular cycloaddition of the bromo derivatives 3 either via azides to fused triazolines or by free radical reaction to pyrrolidines is also described. These reactions provide an entry into functionalized 5 to 8 membered ring heterocycles.
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■ The Eastman’s Reaction Revisited
Benito Alcaide, Carmen Domínguez, Aurelio G. Csákÿ, and Joaquín Plumet*
*Departamento de Química Orgánica, Facultad de Química, Universidad Complutense de Madridas, Ciudad Universitaria, E-28040 Madrid, Spain
Abstract
Several previously unknown 3-acyl-5-alkyl-1-arylpyrazoles, differently functionalized in the 3- and 5- side chains, have been synthesized from appropriate 2,5-disubstituted furans by their reaction with p-nitrobenzenediazonium salts.
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■ Preparation of N-Alkadienyl N-E-2-Arylethenylcarbamates via Sulfoxide Elimination in a Synthetic Approach to Lycorine
Michael E. Jung* and Steven J. Miller
*Department of Chemistry, University of California, Irvine, Irvine, California 92697, U.S.A.
Abstract
N-E-2-Arylethenylcarbamates have been prepared in good yields from N-[2-(phenylthio)-2-arylethyl]carbamates via sulfoxide elimination towards nitrogen.
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■ Recent Work on the Synthesis of Phosphonate-containing, Bone-active Heterocycles
Frank H. Ebetino,* Charles R. Degenhardt, Laura A. Jamieson, and Don C. Burdsall
*Norwich Eaton Pharmaceuticals, Inc., Procter and Gamble Company, P. O. box 191, Norwich, New York 13815, U.S.A.
Abstract
New approaches to the design and synthesis of bone antiresorptive phosphonates have led to the discovery of the cyclic bisphosphonate series and the phosphonoalkylphosphinate heterocyclic series. The latter class, which offers substrates for interesting dianion chemistry, has ben shown to include effective bone-active isosteres of the well known bisphosphonates.
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■ The Synthesis of Carbapenem and Carbacephem Derivatives by a Combination of 4CC with the Chemistry of Oxazoles and N-Boc-carbonamides
Gebhard Neyer, Josef Achatz, Bernhard Danzer, and Ivar Ugi*
*Organisch-Chemisches Institut der Techmisches, Universität München, Münvhen, D-8046 Garching, Germany
Abstract
A synthetic approach to carbapenem and carbacephem derivatives is described. It is based on the formation of the N-carboxymethyl-β-lactam system by a four component condensation, the cleavage of a carbonamide via the N-Boc-carbonamides and esters, and the masking of a carboxyl group as its 4,5-diphenyloxazolyl derivative that is convertible to an N,N-dibenzoylamide by photooxidation.
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■ Reduction of N-Oxide with Baker’s Yeast
Mitsuhiro Takeshita* and Sachiko Yoshida
*Tohoku Pharmaceutical University, 4-4-1 Komatsushima, Aoba-ku, Sendai 981-8558, Japan
Abstract
Reduction of N-oxides with baker’s yeast has been examines. In the reduction of acetylpyridine N-oxides, selective reduction takes place to give chiral pyridylethanol N-oxides.
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■ Syntheses of a Naturally Occurring Hydroxamic Acid and Its Analogues
Akihiro Ohta,* Nobuhiro Takahashi, Yasuko Shirokoma, Kayo Yuasa, Teruo Kurihara, and Hiroshi Miyamae
*Tokyo University of Pharmacy and Life Science, 1432-1 Horinouchi, Hachioji, Tokyo 192-0392, Japan
Abstract
A naturally occurring cyclic hydroxamic acid, isolated from Pseudomonas species, and its analogues were synthesized via six steps starting from 2-hydroxy-3-methoxypyridine. The antimicrobial activity of the synthesized compounds is described.
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■ 2-Oxotetrahydro-1,3-oxazine: A Useful Interamediate for the Preparation of Tetrahydropyridine, Indolizidine, and Quinolizidine Skeletons
Takushi Kurihara,* Yoshitaka Matsubara, Hirotaka Osaki, Sinya Harusawa, and Ryuji Yoneda
*Faculty of Pharmaceutical Science, Osaka University of Pharmaceutical Sciences, 4-20-1 Nasahara, Takatsuki, Osaka 569-1094, Japan
Abstract
Conversion of 2-oxotetrahydro-1,3-oxazines into tetrahydropyridines was applied to the synthesis of indolizidine and quinolizidine alkaloids.
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■ Studies on the Constituents of Beesia calthaefolia, and Souliea vaginata. III. Beesioside IV, a Cyclolampstanol Xyloside from the Rhizomes of B. calthaefolia and S. vaginata
Nobuko Sakurai, Teruo Goto, Masahiro Nagai, Takao Inoue,* and Peigen Xiao
*Hoshi University, 2-4-41 Ebara, Shinagawa-ku, Tokyo 142-8501, Japan
Abstract
A new triterpenol xyloside, beesioside IV, an amorphous powder, [α]D-11.1°, C37H58O11·3/2H2O from the dried rhizomes of Beesia calthaefolis Maxim. and Souliea vaginata (Maxim.) Franch. (both Ranunculaceas) was identified as (20S,24S)-15α-acetoxy-16β,24;20,24-diepoxy-9,19-cyclolanostane-3β,12α,25-triol 3-O-β-D-xylopyranoside on the basis of chemical and physicochemical evidence.
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■ An Easy Synthesis of 4-Alkylthioindoles
Masayuki Murase, Toshihiro Hosaka, and Seisho Tobinaga*
*Showa Pharmaceutical University, 3-3165, Higashi-tamagawagakuen, Machida, Tokyo 194-8543, Japan
Abstract
4-Alkylthio-indoles 7 and 9 were synthesized from 4-thioxo-4,5,6,7-tetrahydroindole (5) in one pot reaction.
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■ Concerning the Intermediacy of Monocyclic β-Lactams in Penicillin Biosynthesis: Synthesis and Attempted Bioconversion of Seco-isopenicillin N
A. Ian Scott,* Ramaswamy Shankaranarayan, and Sung-Kee Chung
*Center for Biological NMR, Department of Chemistry, Texas A & M University, College Station, Texas 77843-3255, U.S.A.
Abstract
The title compound (3a) was synthesized as its dimer by the skeletal rearrangement of protected isopenicillin N-sulfoxide, hydrogenation, hydrolysis of the thiazoline ring, oxidative dimerization and deprotection. The reductive conversion of the dimer to monomer (3a) was clearly demonstrated. Seco-isopenicillin N (3a) gave no bioactive products on incubation with cell-free systems from either Cephalosporium acremonium or Streptomyces clavuligerus.
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■ Nickel-catalyzed Reactions of Thiazoles, Isoxazoles, Oxazolines and Thiazolines with Grignard Reagents
Ernest Wenkert* and Aili Han
*Department of Medicine, University of California, San Diego, 9500 Gilman Drive, La Jolla, CA 92093-0682, U.S.A.
Abstract
Grignard reagents convert thiazoles, isoxazoles, oxazolines and thiazolines into N-vinylimines, β-amino-α,β-unsaturated ketones, tetrahydrooxazoles and tetrahydrothiazoles, respectively, under the influence of phosphine-ligated nickel species. The reaction characteristics and the uncatalyzed reactions are described.
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■ Photoinduced Generation of Glycosyl Cations from Thioglycosides
Gary W. Griffin, Nayanie C. Bandara, Margaret A. Clarke, Wing-Sum Tsang, Per J. Garegg,* S. Oscarson, and B. Azmy Silwanis
*Department of Organic Chemistry, Arrhenius Laboratory, University of Stockholm, SE-10691 Stockholm, Sweden
Abstract
Photochemically induced clevage of thioaryl β-D-glucopyranosides using 1,4-dicyanonaphthalene as an electron-transfer agent, produces glycosyl cations potentially useful in glycosylation reactions.
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■ Mass Spectrometry of Organogermanium Compounds. Fragmentation Process of 1-Germacyclohexane and Their Methyl Derivatives
Katsumi Tanaka and Yoshito Takeuchi*
*Department of Chemistry, The College of Arts & Sciences, The University of Tokyo, Komaba, Meguro-ku, Tokyo 153, Japan
Abstract
The mass spectrometric fragmentation caused by electron impact of germacyclohexane, 3-methyl- and 4-methyl derivatives and their deuteratated species were analyzed. Intially the clevage of Ge-C bond took place, followed by loss of hydrocarbon moieties. The whole fragmentation processes can be explained by the combination of elimination of hydrocarbon moiety(neutral and radical) and hydrogen transfer(McLafferty rearrangement). The base peaks were at m/z 74 (germanium cation radical) in contrast to that of 1,1-dimethyl-1-germacyclohexanes at m/z 89.
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■ Synthesis of Heteroarylquinolines by the Photolysis of 2-, 3-, and 4-Iodoquinolines
Kazue Ohkura, Koh-ichi Seki,* Masanao Terashima, and Yuichi Kanaoka
*Faculty of Pharmaceutical Scicences, Higashinihonngakuen University, 1757 Kanazawa, Toubetu-cho, Ishikari-gun, Hokkaodo 061-0212, Japan
Abstract
Photoreaction of 2-, 3-, and 4-iodoquinolines with five membered heterocycles (i.e. 1-methylpyrrole, pyrrole, furan and thiophene) afforded the corresponding n-(2-heteroaryl)quinolines (n=2,3,4) in appreciable yields.