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
James P. Kutney's Special Issues, Vol. 56, No. 1-2, 2002
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■ Three New Labdane Diterpenoid Glycosides from Conyza blinii
Yanfang Su, Kazuo Koike, Dean Guo,* Jinke Jia, Jiansheng Liu, Junhua Zheng, and Tamotsu Nikaido*
*School of Pharmaceutical Sciences, Toho University, 2-2-1, Miyama, Funabashi, Chiba 274-8510, Japan
Abstract
Three new labdane-type diterpenoid glycosides, blinoside A, blinoside A-15-O-[3”R-hydroxy]octadecanoate and blinoside B, together with a known labdane diterpenoid (E)-8α,15,16-trihydroxy-13-labdene, were isolated and identified from Conyza blinii.
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■ 1,3-Dipolar Cycloaddition of Diazomethane to 1,1-Difluoroallylphosphonates: Application to Synthesis of Cyclopropane Derivatives Having a Diethoxyphosphoryldifluoromethylene Unit
Tsutomu Yokomatsu,* Kenji Suemune, Tetsuo Murano, and Shiroshi Shibuya
*School of Pharmacy, Tokyo University of Pharmacy and Life Science, 1432-1 Horinouchi, Hachioji, Tokyo 192-0392, Japan
Abstract
1,3-Dipolar cycloaddition of diazomethane to (1,1-difluoroallyl)phosphonates was examined to give pyrazolines functionalized by a diethoxyphosphoryldifluoromethylene unit. The pyrazolines were transformed to the cyclopropane derivatives possessing a diethoxyphosphoryl-difluoromethylene functionality by photolysis.
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■ Studies on the Asymmetric Diels-Alder Reaction of Dihydropyridin-2-one with Silyloxydienes
Masamichi Yamanaka, Toshiaki Nagata, Yoshino Nakajima, Atsushi Nishida, and Masako Nakagawa*
*Graduate School of Pharmaceutical Science, Chiba University, 1-33 Yayoi-cho, Inage-ku, Chiba 263-8522, Japan
Abstract
The asymmetric Diels-Alder reaction of dihydropyridin-2-one with 2-triethylsilyloxy-1,3-pentadiene was studied in the presence of chiral aluminum reagents. Menthyloxyaluminum dichloride was the most effective catalyst and gave a hexahydroisoquinolin-2-one derivative in 44% ee as an endo-product after desilylation.
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■ Qinolone Analogues 4. Synthesis ofÅ@1-Methyl-3-trifluoromethylpyridazino[3,4-b]quinoxalin-4(1H)-ones
Yoshihisa Kurasawa,* Izumi Matsuzaki, Waka Satoh, Yoshihisa Okamoto, and Ho Sik Kim
*School of Pharmaceutical Sciences, Kitasato University, Shirokane, Minato-ku, Tokyo 108-8641, Japan
Abstract
The reaction of the quinoxaline N-oxides (7a,b) with 4,4,4-tri-fluoroacetoacetate gave the 1,5-dihydro-3-trifluoromethylpyridazino[3,4-b]quino-xaline-4-carboxylates (15a,b), whose oxidation with nitrous acid afforded the 1,4-dihydro-4-hydroxy-3-trifluoromethylpyridazino[3,4-b]quinoxaline-4-carboxylates (16a,b), respectively. The reaction of compounds (16a,b) with 1,8-diazabi-cyclo[5.4.0]-7-undecene (DBU) provided the 1,5-dihydro-3-trifluoromethylpyridazino[3,4-b]quinoxalin-4-ols (17a,b), whose oxidation with sodium bromate produced the 1-methyl-3-trifluoromethylpyridazino[3,4-b]quinoxalin-4(1H)-ones (6a,b), respectively.
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■ Synthesis and Complexation Behavior of Diaza-18-crown-6 Having Troponyl and Anthryl Groups
Emi Yamamoto, Kanji Kubo,* and Akira Mori*
*Institute of Advanced Material Study, Kyushu University, Kasuga-koen, Kasuga, Fukuoka 816-8580, Japan
Abstract
N-(9-anthrylmethyl)-N’-(tropon-2-yl)diaza-18-crown-6 (4) gave a weak emission, showing that the excited anthracene chromophore was quenched by the diazacrown nitrogen atoms and tropone unit. Diazacrown (4) was found to display unique photophysical properties in the presence of metal salts. Diazacrown (4) exhibited Cu2+ selectivity and in the presence of this cation the host fluorescence intensity was increased by a factor of 7.8.
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■ Synthesis of 2,3-Disubstituted Indoles by Radical Cyclization with Hypophosphorous Acid and Its Application to Total Synthesis of (±)-Catharanthine
Matthew T. Reding, Yosuke Kaburagi, Hidetoshi Tokuyama, and Tohru Fukuyama*
*Graduate School of Pharmaceutical Sciences, University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan
Abstract
Radical cyclization of o-alkenylthioanilides using hypophosphorous acid and AIBN in the presence of Et3N proceeded smoothly to furnish the corresponding 2,3-disubstituted indoles in high yields. Utilizing the newly developed cyclization condition, a stereocontrolled total synthesis of (±)-catharanthine has been completed.
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■ Synthesis and Properties of Terrylenedicarboximide Derivatives
Yukinori Nagao,* Hironobu Iwawaki, and Kozo Kozawa
*Department of Industrial Chemistry, Faculty of Science and Technology, Science University of Tokyo, 2641 Yamazaki, Noda, Chiba 278-8510, Japan
Abstract
Terrylenedicarboximide derivatives were prepared by the coupling of N-alkyl-9-tributylstannylperylene-3,4-dicarboximides with 4-bromo-1,8-naphthalimide derivative and the following ring closure reaction. Spectral properties in solution or in the solid state and the thermal stability of these derivatives were investigated.
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■ Biosynthesis of 2,3-Dihydroxybenzoic Acid in Transgenic Catharanthus roseus Cell Cultures Overexpressing Isochorismate Synthase
Retno A. Budi Muljono, Julian R. Talou, Johannes J. C. Scheffer, and Robert Verpoorte*
*Division of Pharmacognosy, Leiden/Amsterdam Center for Drug Research, Leiden University, Gorlaeus Laboratories, P.O.Box 9502, 2300 RA Leiden, The Netherlands
Abstract
The involvement of isochorismate synthase (EC 5.4.99.6) in the biosynthesis of 2,3-dihydroxybenzoic acid (2,3-DHBA), was confirmed by the incorporation of [1-13C]pyruvate in 2,3-DHBA in a transgenic C. roseus cell line constitutively overexpressing the C. roseus plant ics-gene. The label was mainly in the carboxyl group and at C-3 and C-4, which is consistent with isochorismate as intermediate.
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■ A Novel Approach to [1,2,3]Triazolo[1,5-a]pyrazines
Tjasa Jug, Matjaz Polak, Tomaz Trcek, and Bojan Vercek*
*Faculty of Chemistry and Chemical Technology, University of Ljubljana, Askerceva 5, 1000 Ljubljana, Slovenia
Abstract
A simple method for the preparation of [1,2,3]triazolo[1,5-a]pyrazines involving the cyclization of alkyl 2-benzoylamino-(4,5-dicyano-1H-1,2,3-triazol-1-yl)propenoates (5) is reported.
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■ The Synthesis and Structure of Macrocyclic Pyridinophanes — Potential Anion Receptors
Agnieszka Szumna, Daniel T. Gryko, and Janusz Jurczak*
*Department of Chemistry, Warsaw University, Pasteura 1, 02-093 Warsaw, Poland
Abstract
The simple synthesis of eight di- and tetralactams possessing 2,6-dicarbamoylpyridine moieties linked by aliphatic units is reported. The X-Ray structures of two tetralactams having 22 and 26-membered rings are analyzed in terms of cavity size and potential anion binding ability.
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■ New Solid-supported Reagents (SSRs) for Selective Acylation of Amines
Maurizio Botta,* Federico Corelli,* Elena Petricci, and Catia Seri
*Dipartimento Farmaco Chimico Tecnologico, Università degli Studi di Siena, A. Moro-53100 Siena, Italy
Abstract
The pyrimidine linker (4) was prepared by solid phase synthesis starting from Merrifield resin. Acylation of 4 with different acyl chlorides gave polymer-bound 4-acyloxypyrimidines (2a-c), which proved to be useful solid-supported reagents for the selective acylation of amines. Their use in solution combinatorial chemistry has been also envisaged.
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■ Regioselectivity in the Schmidt Reaction: First Synthesis of Pyrano[3,2-b]azepines
Franc Pozgan, Slovenko Polanc, and Marijan Kočevar*
*Faculty of Chemistry and Chemical Technology, University of Ljubljana, Askerceva 5, SI-1000 Ljubljana, Slovenia
Abstract
The Schmidt reaction of 5,6,7,8-tetrahydro-2H-1-benzopyran-2-ones (1) has been investigated. Derivatives of pyrano[3,2-c]azepines (2) and isomeric pyrano[3,2-b]azepines (3) were isolated by the application of trimethylsilyl azide or sodium azide in a methylene chloride or a chloroform solution in the presence of sulfuric acid. At low temperature products (2) were almost sole products, while at higher temperature derivatives (3) were also isolated in reasonable yields. Derivatives of pyrano[3,2-c]pyridines (5) can be prepared from cyclopenta[b]pyran-2,5-diones (4) employing the same method.
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■ A Highly Sensitive and Specific FDCD Method for Chirality Analysis of Naturally Occurring Pteridines
Ning Chen, Kazuhisa Ikemoto, Takashi Sugimoto, Shizuaki Murata,* Hiroshi Ichinose, and Toshiharu Nagatsu
*Graduate School of Environmental Studies, Nagoya University, Chikusa, Nagoya, Aichi 464-8601, Japan
Abstract
Absolute configurations of 6-(1-hydroxyalkyl)pterin derivatives are determined by fluorescence detected circular dichroism (FDCD) spectroscopy. This method is at least 10 times more sensitive than CD analysis and specific even existence of 10 times excess amounts of chiral sugars or nucleic acids.
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■ Stereoselective 1,3-Dipolar Cycloaddition of an Azomethine Ylide with a Chiral 1,3-Thiazole-5(4H)-thione
Andreas Gebert, Anthony Linden, Grzegorz Mloston, and Heinz Heimgartner*
*Institute of Organic Chemistry, University of Zürich, Winterthurerstrasse 190, CH-8057 Zürich, Switzerland
Abstract
The reaction of cis-1-methyl-2,3-diphenylaziridine (2) with racemic 4-benzyl-4-methyl-2-phenyl-1,3-thiazole-5(4H)-thione (rac-1b) in toluene at 100-105°C gave a single spirocyclic [2+3] cycloadduct (rac-5). Its structure and relative configuration was established by X-Ray crystallography. Starting with enantiomerically pure (R)-1b and (S)-1b, the enantiomers (4R,5R,7S,9R)-5 and (4S,5S,7R,9S)-5, respectively, were formed in a regio- and stereoselective 1,3-dipolar cycloaddition of the in situ generated (E,Z)-configured N-methyl-1,3-diphenylazomethine ylide (4).
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■ Synthesis of 4,4-Difluoro-α-tocopherol Using a Cross-coupling Reaction of Bromodifluoroacetate with Aryl Iodide in the Presence of Copper Powder
Kazuyuki Sato, Takashi Nishimoto, Kei Tamoto, Masaaki Omote, Akira Ando, and Itsumaro Kumadaki*
*Faculty of Pharmaceutical Sciences, Setsunan University, 45-1, Nagaotoge-cho, Hirakata-shi, Osaka 573-0101, Japan
Abstract
Using our new methodology for introduction of a CF2 moiety, 4,4-difluoro-α-tocopherol (2) was synthesized. Thus, 1-iodo-2,5-bis(methoxy-methoxy)-3,4,6-trimethylbenzene (4) was treated with ethyl bromodifluoroacetate (1) in the presence of Cu powder to give a substituted phenyldifluoroacetate (5). Compound (5) was converted to 4,4-difluorochromanol derivative (12). Elongation of the side chain of 12 gave 2.
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■ Further Approaches to Anomalous Carbon Insertion into a Benzene Ring in the Bischler-Napieralski Reaction of Phenolic 2-Phenylformanilides
Tomoko Narioka and Tsutomu Ishikawa*
*Graduate School of Pharmaceutical Science, Chiba University, 1-33 Yayoi-cho, Inage-ku, Chiba 263-8522, Japan
Abstract
Three phenolic 2-phenylformanilides were subjected to Bischler-Napieralski reaction for further examination of anomalous carbon insertion into a benzene ring.
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■ Preparation of 4,7-Dihetaryl-1,2,5-oxadiazolo[3,4-c]pyridines as Red Fluorescent Materials
Hideki Gorohmaru, Thies Thiemann, Tsuyoshi Sawada, Kazufumi Takahashi,* Katsumi Nishi-i, Naoko Ochi, Yoshio Kosugi, and Shuntaro Mataka*
*Instituete of Advanced Material Study, Kyushu University, 6-1, Kasuga-koen, Kasuga 816-8580, Japan
Abstract
A series of 1,2,5-oxadiazolo[3,4-c]pyridines (6, 7, 8 and 10) with thiophene, furan, and benzothiophene rings at the 4 and 7 positions were prepared, in quest of a red fluorescent material useful in OLED devices. Compound (6, 7, 8 and 10) emit fluorescence of orange to red color in solution and in the solid state. 6-Cyano derivatives (6) show a higher quantum yield than the corresponding esters (7), the phenyl derivative (8), and the unsubstituted compound (10). Red EL light at λ = 680 nm was obtained in an OLED device when 4,7-bis(5-phenylthien-2-yl) ester (7h) was used as a dopant emitter.
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■ Synthesis of Azetidine Derivatives Using 1-Azabicyclo[1.1.0]butane
Kazuhiko Hayashi, Shinsuke Hiki, Toshio Kumagai, and Yoshimitsu Nagao*
*Faculty of Pharmaceutical Sciences, University of Tokushima, Sho-machi, Tokushima 770-8505, Japan
Abstract
A THF solution of 1-azabicyclo[1.1.0]butane (2), obtained from 2,3-dibromopropylamine hydrobromide (1), was treated with HCl-EtOH, 48% HBr, ClCO2Et, Ts2O, HCO2H - 2.7N HCl-MeOH, or Ac2O - 3N HCl to give the corresponding 3-monosubstituted and 1,3-disubstituted azetidine derivatives (3-7). Similar treatment of 2 with AcSH afforded 1-acetyl-3-acetylthioazetidine (8), which was converted to 1-(1,3-thiazolidin-2-yl)azetidine-3-thiol hydrochloride (10). The compound (2) and various bromides were heated to furnish 3-bromoazetidine derivatives (12b,c,e,f) and/or N,N-disubstituted 2,3-dibromopropylamines (13a,c-f). The reaction of 2 with benzoyl peroxide or N-bromosuccinimide gave each corresponding 1,3-disubustituted azetidine derivative (14 or 15).
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■ Convenient Synthesis of 3H-Pyrrolo[2,3-c]isoquinolines and 3H-Pyrrolo[2,3-c][1,7]-, 3,4-Benzo[c][1,7]-, and Dihydropyrido[4,3-c][1,8]naphthyridines via Palladium-assisted Nucleophilic Amination
U. Narasimha Rao and Edward R. Biehl*
*Chemistry Department, Southern Methodist University, Dallas, TX 75275, U.S.A.
Abstract
2-Methyl- and 3-ethyl-3H-pyrrolo[2,3-c]isoquinolines and 2-methyl-3H-pyrrolo[2,3-c][1,7]naphthyridines possessing a C-5 saturated heterocyclic ring were prepared from corresponding 4-alkenyl-3-aminoisoquinoline or naphthyridinevia palladium-assisted cyclization under catalytic conditions. Similar treatment of 3-prenyl derivatives of isoquinolines and naphthyridines possessing 6- alkyl groups gave 3,3,-dimethyl-3,4-dihydrobenzo[c]- and 3,4-dihydropyridino[4,3-c]naphthyridines, respectively. The Hegedus precursors were synthesized by alkenylation of 2-cyanomethylbenzonitrile or 3-cyanomethylpyridine-2-carbonitrile followed by basemediated cyclization of α-alkenyl derivatives so formed using lithium amides or alkyllithiums.
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■ New Chiral Pyrrolidinyl- and 2-Azanorbornyloxazolidine Ligands for Enantioselective Addition of Diethylzinc to Aldehydes
Hiroto Nakano,* Yuko Okuyama, Kazuyuki Fushimi, Ryo Yamakawa, Daisuke Kayaoka, and Hiroshi Hongo*
*Tohoku Pharmaceutical University, 4-4-1 Komatsushima, Aoba-ku, Sendai 981-8558, Japan
Abstract
A new type of optically active ligands, pyrrolidinyl- (3a-c) and 2-azanorbornyloxazolidines (6a-d) were synthesized and their abilities as ligands were examined in the enantioselective addition of diethylzinc to aromatic and aliphatic aldehydes to give optically active secondary alcohols of up to 83% ee.
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■ Indium-mediated Reductive Cyclizations in Aqueous Ethanol: Highly Efficient Synthesis of Heterocyclic Compounds of Biological Interests
Bimal K. Banik,* Indrani Banik, Linda Hackfeld, and Frederick F. Becker
*The University of Texas, M. D. Anderson Cancer Center, 1515 Holcombe Blvd., Houston, TX 77030, U.S.A.
Abstract
Indium/ammonium chloride in the presence of aqueous ethanol was found to be very effective in reductive cyclization reactions leading to the development of several heterocyclic compounds of biological significance.
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■ [4+2] Cycloadditions of o-Thioquinones with Alkynes and Arylalkenes: a Facile Synthesis of Benzoxathiins
Vijay Nair* and Bini Mathew
*Organic Chemistry Division, Regional Research Laboratory, Council of Scientific and Industrial Research (CSIR), Trivandrum-695 019, India
Abstract
o-Thioquinones generated in situ from o-hydroxybenzothiophthalimides underwent facile [4+2] cycloaddition reaction with alkynes and alkenes to afford benzoxathiin derivatives.
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■ Synthesis of Modified Analogues of Taxol C,D Subunits from Furan
Odón Arjona, María L. León, Roberto Menchaca, and Joaquín Plumet*
*Universidad Complutense, Facultad de Química, Dpto. de Química Orgánica I, 28040 Madrid, Spain
Abstract
The synthesis of two modified analogues of the C,D subunits of taxol, using a furan derivative as precursor, is reported.
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■ Synthesis of Amino Acid Derivatives of 6-Aminoquinoline Antimalarial Agents
Supat Jiranusornkul,* Busaban Sirithunyalug, Hideo Nemoto, and Hiroki Takahata*
*Tohoku Pharmaceutical University, 4-4-1 Komatsushima, Aoba-ku, Sendai 981-8558, Japan
Abstract
Six new 6-aminoquinoline derivatives with amino acid in basic side chain were synthesized in order to modify their biological activities.
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■ A Simple and Facile Synthesis of Azuleno[1,2-d]pyrazoles from 1-Acetyl-2-methoxyazulene
Dao-Lin Wang and Kimiaki Imafuku*
*Department of Chemistry, Faculty of Science, Kumamoto University, Kurokami 2-39-1, Kumamoto 860-8555, Japan
Abstract
1-Acetyl-2-methoxyazulene (1) reacted with arylhydrazines (2a-h) under refluxing in ethanol to give 1-aryl-3-methylazuleno[1,2-d]pyrazoles (3a-h) in moderate to high yields, except for the low yield of azuleno[1,2-d]pyrazole (3g).
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■ Cyclopropane Ring Formation through Enantioselective Deprotonation of Cs-Symmetric Cyclohept-4-enone Oxides
Hitoshi Abe,* Takenori Tsujino, Daisuke Tsuchida, Setsuo Kashino, Yasuo Takeuchi, and Takashi Harayama*
*Faculty of Pharmaceutical Sciences, Okayama University, 1-1-1 Tsushima-naka, Okayama 700-8530, Japan
Abstract
Using a chiral lithium amide base, the asymmetric deprotonation reaction of Cs-symmetric cyclohept-4-enone oxides was examined to form an optically active cyclopropane compound.
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■ Isolation and Characterization of UDP-glucosyltransferase in the Cultured Cells of Nicotiana tabacum
Shin-ya Yamane, Kei Shimoda, Takeshi Fujino, Shinji Ohta, and Toshifumi Hirata*
*Department of Mathematical and Life Sciences, Graduate School of Science, Hiroshima University, 1-3-1 Kagamiyama, Higashi-hiroshima, Hiroshima 739-8526, Japan
Abstract
A glucosyltransferase, catalyzing the transfer of glucose from UDP-glucose to hydroxycoumarins, was isolated from the cultured cells of Nicotiana tabacum. The glucosyltransferase was purified to electrophoretic homogeneity by a procedure involving Sephadex G-25, Agarose-gel affinity, and Sephadex G-200 columns; the enzyme has molecular mass of 61 kDa and pH optimum at 8.0 and the activity was inhibited by divalent metal ions such as Co2+ and Zn2+. The enzyme glucosylated preferentially 7-hydroxyl group of hydroxycoumarins.
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■ Synthetic Studies on Indoles and Related Compounds 50. Improved Synthesis of 7,9-Didecarboxymethoxathine
Hideharu Suzuki, Toshiko Watanabe, Yuusaku Yokoyama, and Yasuoki Murakami*
*School of Pharmaceutical Sciences, Toho University, 2-2-1, Miyama, Funabashi, Chiba 274-8510, Japan
Abstract
An improved synthesis of 7, 9-didecarboxymethoxathine (2, R=H) is described.
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■ Synthesis of Non-peptidic Tryptamine Derivative (THS-12) which Stimulates TPO Responsive Cell Growth (Synthetic Studies on Indoles and Related Compounds 51)
Hideharu Suzuki, Tomoko Furukawa, Chiaki Yamada, Ichiro Shibuya, Masateru Kurumi, Tetsuo Yokoyama, and Yasuoki Murakami*
*School of Pharmaceutical Sciences, Toho University, 2-2-1, Miyama, Funabashi, Chiba 274-8510, Japan
Abstract
A number of synthetic indole compounds were examined for in vitro TPO responsive cell proliferation assay using BaF/mpl cell. Among these compounds 3-(2-aminoacetyl)-1-phenylsulfonylindole hydrochloride (7, THS-12), which was synthesized via α-bromination of 3-acetyl-1-phenylsulfonylindole followed by amination with hexamethylenetetramine, stimulated strongly cell growth. During the synthetic study we found that the Friedel-Crafts reaction of 1-phenylsulfonylindole (1) with chloroacetyl chloride using AlCl3 unexpectedly gave 6-chloroacetyl-1-phenylsulfonylindole as a main product.
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■ A Study for Palladium-catalyzed Chemoselective Vinylation at C-3 Position of 4-Bromo-1-tosylindole
Yuusaku Yokoyama,* Kazuhiro Tsuruta, and Yasuoki Murakami*
*School of Pharmaceutical Sciences, Toho University, 2-2-1, Miyama, Funabashi, Chiba 274-8510, Japan
Abstract
Palladium-catalyzed direct activation of carbon-hydrogen bond at C-3 position of 4-bromo-1-tosylindole (1) was investigated. The reaction of 1 with ethyl acrylate (4) in the presence of 0.1 eq. of Pd(OAc)2 and MnO2-Cu(OAc)2-O2 system afforded C-3 vinylated product (5) in 52% yield, and by-products (6 and 7) that were formed by the Michael addition of AcOH or H2O to 5, were obtained in 17% and 7% yields respectively.