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
Edward C. Taylor's Special Issues, Vol. 35, No. 2, 1993
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■ γ-Cyclodextrins Bearing a Pyrenylamide Moiety. The Effect of Photoexcited-State Acid-Base Equilibrium of Appended Chromophone on Their Guest Binding
Iwao Suzuki, Yoshinobu Sakurai, Masahiro Ohkubo, Maki Ito, Tetsuo Osa,* and Akihiko Ueno
*Pharnaceutical Institute, Tohoku University, Aramaki, Aoba-ku, sendai 980-8578, Japan
Abstract
γ-Cyclodextrins bearing a pyrenylamide moiety at primary or secondary hydroxyl side (1 and 2, respectively) showed red-shifted fluorescence as well as normal fluorescence in a solution of pH below 3. This red-shifted fluorescence was emitted from the pyrenylamide moiety protonated in the excited state. Guest binding ability of 2 was markedly affected by the protonation, while that of 1 was hardly affected.
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■ Synthesis of Cyclopentadienyl-ene-1,2-dithiolatocobalt Complexes and Coupled Proton-Electron Transfer in a Substituted Quinaxalinyl Derivative
Elaine M. Armstrong, Michael S. Austerberry, Jacqueline H. Birks, Roy L. Beddoes, Madeleine Helliwell, John A. Joule, and C. David Garner*
*Department of Chemistry, University of Manchester, Oxford Road, Manchester, M13 9PL, U.K.
Abstract
A series of cyclopentadienyl-ene-1,2-dithiolatocobalt complexes, [(η5-C5H5)Co(S2C2RH)], has been prepared. The derivative in which quinoxalin-2-yl is bound to the dithiolene manifests novel electrochemical behaviour in acidic media which is consistent with a coupling of metal-centered electron addition to protonation of a pyrazine ring nitrogen.
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■ Photocycloaddition of 2'-Deoxyribonuculeoside to 2,3-Dimethly-2-butene
Naoki Haga, Ichiro Ishikawa, Masaya Kinumura, Hiroaki Takayanagi, and Haruo Ogura*
*School of Pharmaceutical Sciences, Kitasato University, 5-9-1, Shirokane, Minato-ku, Tokyo 108-8641, Japan
Abstract
Photosensitized cycloaddition of 2,3-dimethyl-2-butene to 2’-deoxyuridine, thymidine and 5-fluoro-2’-deoxyuridine by the uv irradiation in acetone have been studied. From the respective reactant, a pair of diastereomers which has a cyclobutane ring were formed. However in each reaction one of the two isomers could be isolated and purified by recrystallization.
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■ An Effecient Synthesis of 2-Aroly-1H-indoles
Yohko Takeda, Akiko Kikuchi, and Masanao Terashima*
*Faculty of Pharmaceutical Scicences, Higashinihonngakuen University, 1757 Kanazawa, Toubetu-cho, Ishikari-gun, Hokkaodo 061-0212, Japan
Abstract
2-Aroyl-1H-indoles were directly obtained by the reaction of 1-(N-aroylcarbamoyl)indoles, prepared from 1-(2-oxazolinyl)indole and aroyl chlorides, with LDA.
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■ Stereoselective Synthesis of Diamino Diol Derivaties with C2-Axis of Symmetry
Tsutomu Yokomatsu, Kenjio Suemune, and Shiroshi Shibuya*
*Tokyo University of Pharmacy and Life Science, 1432-1 Horinouchi, Hachioji, Tokyo 192-0392, Japan
Abstract
An efficient and stereocontrolled synthesis of C2-symmetric diamino diol derivatives (7) was achieved through selective opening of N-Boc bis-aziridine (6), prepared from D-mannitol via cyclic sulfate(4).
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■ Vicarious Nucleophilic Substitution of 1,2,3-Triazines
Takashi Itoh, Kazuhiro Nagata, Mamiko Okada, and Akio Ohsawa*
*School of Pharmaceutical Sciences, Showa University, 1-5-8 Hatanodai, Shinagawa-ku, Tokyo 142-8555, Japan
Abstract
Vicarious nucleophilic substitution of 1,2,3-triazinium 2-dicyanomethylides with 1-chloromethyl phenyl sulfone proceeded to give corresponding 5-substituted derivatives. Dicyanomethylene group was readily eliminated by radical reaction to afford 5-phenylsulfonylmethyl-1,2,3-triazines.
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■ A Unified Synthetic Strategy for Elaboration of the DEF Tricyclic Subunit Common to the Austalide Mycotoxins
Leo A. Paquette* and Matthias M. Schulze
*Evans Chemical Laboratories, The Ohio State University, 120 W. 18th Avenue, Columbus, Ohio 43210, U.S.A.
Abstract
Tricycle (19), representing the DEF subunit common to all known austalide mycotoxins, has been economically synthesized from 2,3-dihydropyran in 8 steps via several highly stereo- and regioselective transformations.
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■ 1,3-Dipolar Cycloaddition Reactions Involving Captodative Olefins
Rogelio Jiménez, Lucelia Pérez, Jaoquín Tamariz, and Hector Salgado*
*Departamento de Química Orgánica, Escuela Nacional de Ciencias Biológicas, I. P. N., Prol. Carpio y Plan de Ayala S/N,11340, Mexico, D.F.
Abstract
A series of arylnitrile oxides (6a-e) were reacted with captodative olefins (4) to yield 5-acetyl-3-arylisoxazoles. No intermediate isoxazolines were formed, the olefins thus behaved as acetylene equivalents. A plausible explanation for the observed regioselectivity in the process is offered as well.
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■ Synthesis of Pyrano[4,3-b]benzodiazepine and Pyrano[4,3-b]quinoline Using 4-Chloro-3-(1-chlorovinyl)-6-methyl-2H-pyran-2-one and 4-Chloro-3-ethynyl-6-methyl-2H-pyran-2-one
Yutaka Azuma,* Atsuko Sato, and Mieko Morone
*Tohoku Pharmaceutical University, 4-4-1 Komatsushima, Aoba-ku, Sendai 981-8558, Japan
Abstract
Reaction of dichloropyrone (1) and chloroethynylpyrone (2) with o-phenylenediamine and m-phenylenediamine give pyranobenzodiazepine (3) and pyranoquinoline (5), respectively. Treatment of 1 and 2 with p-phenylenediamine yield aminoethynylpyrone (6), which is a key product in the readion of 1 and 2 with phenylenediamines.
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■ Enzyme-catalyzed Synthesis of Biologically Active (S)-Nilvadipine
Hirosato Ebiike, Yumi Ozawa, Kazuo Achiwa,* Yoshihiko Hirose, Kinya Kariya, Ikuharu Sasaki, and Yoshiaki Kurono
*Schol of Pharmaceutical Sciences, University of Shizuoka, 52-1 Yada, Shizuoka 422-8526, Japan
Abstract
Optically active 2-hydroxymethyl-1,4-dihydropyridine was obtained by lipase-catalyzed transesterification of isopropyl methyl 1,4-dihydro-2-hydroxymethyl-6-methyl-4-(3-nitrophenyl)-3,5-pyridinecarboxylate. This chiral dihydropyridine was readily converted into biologically active (S)-nilvadipine.
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■ Isolation of (-)-Preorixine, a Postulated Biosynthetic Key Intermediate of (+)-Orixine and Related Quinoline Alkaloids, from the Stems of Orixa japonica
Shinji Funayama, Takahiro Kageyama, Kiyoshi Murata, Michiko Adachi, and Shigeo Nozoe*
*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan
Abstract
A prenyl quinoline alkaloid (-)-preorixine was isolated from the stems of Orixa japonica (Rutaceae) and its structure was elucidated to be (-)-3-(2S,3-epoxy-3-methylbutyl)-2,4-dimethoxy-7,8-methylenedioxyquinoline. (-)-Preorixine is postulated as a biosynthetic key intermediate of (+)-orixine and related compounds.
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■ Formation of Oxygen Heterocycles from Alkynes Catalyzed by Ru3(CO)12
Naim Menashe and Youval Shvo*
*School of Chemistry, Raymond and Beverly Sackler Faculty of Exact Sciences, Tel Aviv university, Tel Aviv, 69978, Israel
Abstract
When dimethyl acetylenedicarboxylate and 2-cyanophenylphenylacetylene were each reacted with acetic acid under catalysis of Ru3(CO)12, 2,3,4-tricarbomethoxy-α-pyrone (1) and 3-phenylisocoumarin (3) were formed in good yields.
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■ The Stereoselective Hydrogenation of Nepetalactoles. The Role of C1 Alkoxyl Groups on the Stereoselectivity
Masaharu Kigawa, Masahide Tanaka, Takao Katsuhara, Koh Sugama, Masao Maruno, Hiroshi Mitsuhashi, and Takeshi Wakamatsu*
*Tsumura Reserach Institute for Biology and Chemistry (TRIBIC), 3586 Yoshiwara, Ami-machi, Inashiki-gun, Ibaraki 300-1192, Japan
Abstract
The stereoselective hydrogenation of nepetalactol and its derivatives was examined. From the stereochemical outcome and the conformational analyses of starting materials, it was concluded that, in the hydrogenation of nepetalactols, the most important factor which determined the steric course of reaction is the configuration of C1 position which carries the alkoxyl group.
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■ Synthesis of 3-Hydroxy-2,3,4,5-tetrahydro-1,5-benzothiazepines
Michinori Karikomi, Shouzou Yamori, and Takashi Toda*
*Department of Applied Chemistry, Faculty of Engineering, Utsunomiya University, 7-1-2 Yoto, Utsunomiya 321-8585, Japan
Abstract
New general synthetic methods of benzothiazepine derivatives were studied. Treatment of 2-(1-haloalkyl)oxiranes (1) with 2-aminothiophenol in the presence of a base provides a variety of benzothiazepine derivatives (4) in excellent yields. The reaction is assumed to proceed through cyclization of an oxirane intermediate (3).
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■ Selective Sinthesis of Five and Six Membered Cyclic Carbamates by the Reaction of 2-(1-Haloalkyl)oxiranes with Carbon Dioxide and Aliphatic Primary Amines
Masaaki Yoshida, Masabumi Ohshima, and Takashi Toda*
*Department of Applied Chemistry, Faculty of Engineering, Utsunomiya University, 7-1-2 Yoto, Utsunomiya 321-8585, Japan
Abstract
The reaction of 2-(1-haloalkyl)oxiranes with carbamate salts selectively gave perhydrooxazin-2-ones at neutral conditions and oxazolidin-2-ones at basic. Those reactions proceeded stereospecifically and the mechanisms were discussed.
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■ Stereoselective Synthesis of Highly Functionalized γ-Lactones via Iodolactonization
Manfred T. Reetz* and Erik H. Lauterbach
*Max-Planck-Institut für Kohlenforschung, Kaiser-Wilhelm-Platz 1, 4330 Mülheim/Ruhr, Germany
Abstract
Chiral γ-amino α,β-unsaturated carboxylic acids (5) derived from L-amino acids undergo diastereofacially selective iodolactonization with formation of the highly functionalized lactones (7).
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■ Theoretical Study of Mechanism and Stereoselectivity of the Ring Opening of Formyloxirane
Kensuke Nakamura and Kendall N. Houk*
*Department of Chemistry and Biochemistry, University of California, 405 Hilgard Avenue, Los Angels, CA 90024, U.S.A.
Abstract
The stereochemistry and reaction mechanism of the thermal ring opening of formyloxirane and subsequent cyclization were studied by using the ab initio molecular orbital calculations. Stationary points along lowest energy pathways, including the unstable carbonyl ylide intermediate were located.
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■ β-Lactam Formation via Enolate Addition: An Unexpected Methylenation Reaction
Maghar S. Manhas,* Ashok G. Chaudhary, Vegesna S. Raju, Ernest W. Robb, and Ajay K. Bose
*Department of Chemistry and Chemical Engineering, Stevens Institute of Technology, Castle Point on the Hudson, Hoboken, NJ 07030, U.S.A.
Abstract
The condensation of ethyl phenylacetate or ethyl β-hydroxyburyrate with Schiff bases in presence of an excess of lithium diisopropylamide or lithium hexamethyldisilazide leads to unsaturated amides instead of the expected β-lactams.
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■ Highly Regioselective Alkylation of Pteridine
Shizuaki Murata,* Kenji Kiguchi, and Takashi Sugimoto
*Laboratories of Biophysics and Bioorganic Chemistry, Graduate School of Human Informatics, Nagoya University, Chikusa, Nagoya 464-8601, Japan
Abstract
Reaction of 2-amino-4-butoxypteridine with a Grignard reagent or an alkyllithium followed by iodine oxidation gives the 7-substituted pteridine, regioselectively.
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■ A Practical Prepraration of Δ1-2-Substituted and Δ1-2,3-Disubstituted Pyrrolines
Mark L. Haslego, Cynthia A. Maryanoff, Lorraine Scott, and Kirk L. Sorgi*
*Chemical Development Department, The R. W. Johnson Pahramceutical Research Institute, Spring House, PA 19477-0766, U.S.A.
Abstract
Addition of N-vinylpyrrolidinone and an ester to NaH in THF effects acylation and affords keto lactams (1) in high yields. Hydrolysis of 1 in strong acid generates Δ1-2-substituted pyrrolines (2) in good yield. Keto lactams (1) can be further alkylated and hydrolyzed to produce Δ1-2,3-disubstituted pyrrolines (4) in good isolated yield.
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■ Mechanism and Stereochemical Implications of the Reaction of an Oxazolium-5-oxide with 1,2-Dicyanocyclobutene. An AM1 Study
Cynthia A. Maryanoff and Ignatius J. Turchi*
*Chemical Development Department, The R. W. Johnson Pahramceutical Research Institute, Raritan, NJ 08869, U.S.A.
Abstract
Oxazolium-5-oxide (1) cycloadds to 1,2-dicyanocyclobutene (2) to give the imino-acid (3) and the dihydroazepine (4). AM1 molecular orbital calculations were carried out on the reaction in order to rationalize the observed stereochemistry of 3 and to further elucidate the overall reaction mechanism leading to 3 and 4.
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■ Preparation of 3,4-Diaryl-4,5-dihydro-1H-1,2,4-triazole-1-N-phenylcarboxamides
Donald J. Dumas*
*Du Pont Agricultural Products, E. I. du Pont Nemours Company, Delaware 19898, U.S.A.
Abstract
N3-Arylbenzamidrazone (5) reacts with aldehydes and ketones to give the corresponding hydrazones (6) rather than the tautomeric 4,5-dihydro-1H-1,2,4-triazoles (7). Treatment of the hydrazones (6) with α,α,α-trifluoro-p-tolyl isocyanate gives 3,4-diaryl-4,5-dihydro-1H-1,2,4-triazole-1-carboxamides (8). This suggests that, in solution, hydrazones (6) exist in equilibrium with low levels of the more nucleophilic 4,5-dihydro-1H-1,2,4-triazoles (7) which are trapped by isocyanate to give triazolines of formula (8).
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■ Reaction of Diols and Triols with Trialkyl Orthoesters: Facile One-Pot Formation of Oxacyclic Compounds from Triols
Hiromichi Fujioka, Hidetoshi Kitagawa, Michinori Kondo, Naoki Matsunaga, Shinji Kitagaki, and Yasuyuki Kita*
*Faculty of Pharmaceutical Sciences, Osaka University, 1-6 Yamadaoka, Toyonaka, Osaka 560-0043, Japan
Abstract
Reaction of diols and triols with trialkyl orthoesters was studied and facile one-pot formation of oxacyclic compounds from triols was developed.
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■ Chelation Controlled Nucleophilic Addition of Tetronic Acid Dianion to Aldimines: Towards the Stereoselective Construction of β-Amino Alcohols
Toshio Honda,* Tomohisa Hayakawa, Toshio Yamada, Hirotsune Kondoh, and Hiromasa Nagase
*Institute of Medicinal Chemistry, Hoshi University, 2-4-41 Ebara, Shinagawa-ku, Tokyo 142-8501, Japan
Abstract
Nucleophilic addition reaction of tetronic acid dianion, derived from tetronic acid with lithium diisopropylamide, to aldimines was found to proceed in a stereoselective manner providing syn adducts predominantly via the six-membered chelation transition states.
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■ Metal Binding by the Trisoxazole Portion of the Marine Natural Product Dihydrohalichondramide
D. Martin James, Edward Wintner, D. John Faulkner, and Jay S. Siegel*
*Department of Chemistry (D-006), University of California, San Diego, La Jolla, CA 92093-0682a, U.S.A.
Abstract
Metal binding to the oxazole portion of dihydrohalichondramide (1), trisoxazole (2), and diphenyloxazole (3) are studied by fluorescence quenching and nmr techniques. The trisoxazole conformation is modeled by semiempirical computations. 1-3 are found to be relatively weak binders which do not exhibit a significant chelate effect. The biological action of 1 is not related to metal binding.
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■ New Synthesis of Piperidine Derivatives via the Chromacyclobutane
Susumu Watanuki and Miwako Mori*
*Faculty of Pharmaceutical Sciences, Hokkaido University, Sapporo 060-0812, Japan
Abstract
Piperidine derivatives were synthesized from the enynes and Fischer chromium carbene complex via chromacyclobutanes in moderate yields and the reaction course was controlled by the substituents on the double bond of the enynes.
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■ An Unusual Synthesis of Nicotinamides
Philip M. Harrington*
*American Cyanamid Company, Agricultural Research Division, P. O. Box 400, Princeton, NJ 08543-0400, U. S. A.
Abstract
Reaction of 2,3-pyridinedicarboxylic anhydride (1) with a substituted aniline (2) in acetic acid gave rise to a mixture of two products. These two products were identified as the cyclic imide (4) and nicotinamide (5). A mechanistic scheme consistent with empirical observations is proposed.
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■ Directed 2-Metalation of N,N-Diethyl O-3-(4-Trimethylsilyl)pyridyl Carbamate. A Silicon Protection Route for Highly Substituted Pyridines
Masao Tsukazaki and Victor Snieckus*
*Guelph-Waterloo Centre for Graduate Work in Chemistry, University of Waterloo, Waterloo, Ontario, N2L 3G1, Canada
Abstract
LiTMP metalation of N,N-diethyl O-3-(4-trimethylsilyl)pyridyl carbamate (4) followed by quenching with a number of carbon and heteroatom electrophiles affords a variety of 2-substituted derivatives (5) (Table 2) thus providing a versatile new methodology for the synthesis of polysubstituted pyridines.
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■ Synthesis of 2,3-Fused Quinolines from 3-Substituted Quinoline 1-Oxides. Part III. Intramolecular Cyclization of Quinoline 1-Oxides Bearing Active Methylene Groups at the 3-Position in the Presence of Acetic Anhydride
Yutaka Miura,* Yasuo Fujimura, Sakae Takaku, and Masatomo Hamana
*Exploratory Laboratories, Chugai Pharmaceutical Company, Ltd., 1-135 Komakado, Gotemba, Shizuoka 412-835, Japan
Abstract
3-N-Alkylcyanoacetamidoquinoline 1-oxides (3a and 3c) react with Ac2O at room temperature in chloroform to afford 1-alkyl-3-cyano-4H-pyrrolo[3,2-b]quinolin-2-ones (4a and 4c). The cyclization of 3-N-alkylethoxycarbonylacetamidoquinoline 1-oxides (3b and 3d) occurs upon heating with Ac2O at 60°C. 3-(3,3-Dicyanopropoxy)quinoline 1-oxide (5) also cyclizes to the pyranoquinoline (6) when treated with Ac2O at room temperature in chloroform-DMF.
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■ Onium Ions are not on the Reaction Coordinate in the Formation of Heterocycles via Electrophile-induced Alkenol Cyclizations
James Sperka and Dennis C. Liotta*
*Department of Chemistry, Emory University, 1521 Pierce Drive Atlanta, Georgia 30322, U.S.A.
Abstract
Semi-empirical molecular orbital methodology was used to determine the reaction surfaces for competitive intramolecular bromoetherification and intermolecular bromohydrin reactions. These reactions do not proceed through a bromonium ion intermediate. Instead, the additions involve the formation of a weak olefin / Br+ Π-complex which is subsequently captured by a proximate nucleophile.