HETEROCYCLES
An International Journal for Reviews and Communications in Heterocyclic ChemistryWeb Edition ISSN: 1881-0942
Published online by The Japan Institute of Heterocyclic Chemistry
Regular Issue
Vol. 29, No. 3, 1989
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■ Peperomins A, B, and C, Novel Secolignans from Peperomia japonica
Chiu-Ming Chen,* Feng-Yih Jan, Ming-Tyan Chen, and Tsong-Jen Lee
*Department of Chemistry, National Tsing Hua University, Hsinchu, Taiwan 30013, Taiwan, R.O.C.
Abstract
Three novel lignans having unusual seco structure, peperomins A, B and C were isolated from the fresh whole plant of Peperomia japonica Makino (Piperaceae). The structures of peperomins A, B and C were established as I, II and III, respectively, on the basis of spectroscopic and crystallographic evidence.
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■ A Convenient Reductive Cyclisation of 2-Nitro-β-nitrostyrenes to Indoles
Sundramoorthi Rajeswari, Kevin J. Drost, and Michael P. Cava*
*Department of Chemistry, The University of Alabama, Box 870336, Tuscaloosa Alabama 35487-0336, U.S.A.
Abstract
A simple synthesis of a variety of 2,3-unsubstituted indoles containing alkoxy and acetoxy groups has been developed. This method involves the reductive cyclisation of 2,β-dinitrostyrenes with ammonium formate in the presence of a catalytic amount of Pd/C in refluxing methanol, and affords indoles in good to excellent yields.
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■ Glycosylaziridine Derivatives
Jean M. J. Tronchet* and Mohamed A. M. Massoud
*Institute of Pharmaceutical Chemistry, University of Geneva, 30, Quai e.-Ansermet, CH-1211 Geneva 4, Switzerland
Abstract
Addition of ammonia to the bromoenoses Ia-e afforded the corresponding secondary dissymmetric aziridines IIa-e respectively. The stereochemistry of their ring opening and ring expansion to δ2-oxazolines has been studied and the absolute configuration of the two newly obtained asymmetric carbon atoms was established.
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■ An Efficient Total Synthesis of AC-5-1: Novel 5-Lipoxygenase Inhibitor Isolated from Artocarpus communis
Jun Nakano,* Katsuhiro Uchida, and Yasuo Fujimoto
*Kyoto Research Institute, Kaken Pharmaceutical Co., Ltd., Shinomiya, Minamikawara-cho, Yamashina-ku, Kyoto 607-8042, Japan
Abstract
The first total synthesis of the highly potent 5-lipoxygenase inhibitor, AC-5-1, from Artocarpus communis has been accomplished by using the oxazoline method of Meyers as a key step.
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■ Study on the Structure of Pseudocrown Ether Formed in the Reaction of Ionophore 6-O-BPY1 and Cu+ by 500 MHz 1H Nmr Spectrometry
Tatsuya Nabeshima, Tadashi Inaba, and Naomichi Furukawa*
*Department of Chemistry, University of Tsukuba, 1-1-1 Ten-nodai, Tsukuba-shi, Ibaraki, 305-8571, Japan
Abstract
The structures of ionophore 6-O-bpy 1 and 1-Cu+ complex were studied by 500 MHz 1H nmr spectrometry. Characteristic downfield and upfield shifts of the aromatic
protons, and the methyl and the methylene protons in the picolyl moiety support strongly generation of pseudocrown structure in the 1-Cu+ complex.
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■ Synthesis of 2,2-Disubstituted Succinimides and Their Regioselective Thiocarbonylation Reaction
Yoshiyuki Kosugi,* Masako Kosugi, and Fumiko Hamaguchi
*Tokyo University of Pharmacy and Life Science, 1432-1 Horinouchi, Hachioji, Tokyo 192-0392, Japan
Abstract
2,2-Dialkoxy- and 2,2-bis(alkylthio)succinimide (3a-c and 3g) were prepared from 2,3-dibromosuccinimide by the reaction with alkoxide or thiolate anion. In contrast to most 2,2-disubstituted succinimides, thiocarbonylation reaction of the imides bearing ethylenedioxy group with Lawesson reagent occurred at the more hindered carbonyl group to give monothioimides (6c and 6d) as major products.
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■ Synthesis, Crystal Structure, and Conformational Property of N, N’-Dimethyl-1,11-(methanoaminomehtano)-5H,7H-dibenzo[b,g][1,5]-thiazocine: a New Heterocyclic system
Hisashi Fujihara, Nobuo Oi, Ryouichi Akaishi, Takatoshi Kawao, and Naomichi Furukawa*
*Department of Chemistry, University of Tsukuba, 1-1-1 Ten-nodai, Tsukuba-shi, Ibaraki, 305-8571, Japan
Abstract
A new heterocyclic compound, N,N’-dimethyl-1,11-(methanoaminomethano)-5H,7H-dibenzo[b,g][1,5]thiazocine has been synthesized; the eight-membered ring is in the rigid chair-chair conformation.
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■ Enantiocontrolled Approach to Natural Products Utilizing (S)-O-Benzylglycidol as Common Chiral Precursor
Seiichi Takano,* Yoshinori Sekiguchi, and Kunio Ogasawara
*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan
Abstract
An enantiocontrolled route to the aggregation pheromone of European elm bark beetle (12), the sex pheromone of cigarette beetle serricornin (15), and the spiroketal segment (24) of the sixteen-membered macrolide antibiotics milbemycins and avermectins is described using the intermediates derived from (S)-O-benzylglycidol (1) as common chiral precursor.
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■ Enantioselective Synthesis of 2,2-Disubstituted 3-Cyclopentenone from 3-Alkyl-4-thianones
Haruo Matsuyama,* Yoshihiro Ebisawa, Michio Kobayashi, and Nobumasa Kamigata
*Department of Chemistry, Faculty of Science, Tokyo Metropolitan University, Hachioji, Tokyo 192-0397, Japan
Abstract
Enantioselective Synthesis of quaternary carbon centers through Michael-type alkylation of chiral imines of 3-methyl-4-thianone and successive regioselective synthesis of chiral 2,2-dialkyl-3-cyclopentenone via Ramberg-Bäcklund reactions are reported.
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■ α-Allylation of β-Tetronic Acids and Chirality Transfer via the 4-Oxygenated 2(5H)-Furanone System
Takefumi Momose,* Naoki Toyooka, Hiromi Fujii, and Hironobu Yanagino
*Faculty of Pharmaceutical Sciences, Kinki University, 3-4-1, Kowakae, Higashi-Osaka 577-8502, Japan
Abstract
α-Allylation of the β-tetronate system was accomplished by direct attack of allyl halide on C-3 of the system in the presence of potassium carbonate in N,N-dimethylformamide or the Claisen rearrangement of allyl tetronates concomitantly formed in the preceding direct allylation. The chirality of natural L- amino acids was transferred into the β-tetronic acid system at the α-position via initial incorporation into the γ-position and subsequent α-allylation by application of analogous sequence of reactions.
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■ Intramolecular Cyclization of Methylthiofuropyridones
Takeaki Naito,* Okiko Miyata, and Ichiya Ninomiya
*Kobe Women’s College of Pharmacy, Motoyamakita, Higashinad, Kobe, Hyogo 658, Japan
Abstract
Methylthiofuropyridone 4 has been proved as a potential synthon for the construction of indoloquinolizidine structure by the intramolecular cyclization involving methylthio and lactam carbanyl groups.
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■ Azafluorene and Aporphine Alkyloids from Polyalthia longifolia
Yang-Chang Wu*
*School of Pharmacy, Kaohsiung Medical College, 100 Shih Chuen 1st Rd., Kaohsiung 80708, Taiwan, R.O.C.
Abstract
A novel azafluorene alkaloid, polylongine (5-hydroxy-6-methoxy-1-methyl-4-azafluoren-9-ol) (1) and three new aporphine N-oxide alkaloids named (+)-O-methylbulbocapnine β-N-oxide (2), (+)-O-methylbulbocapnine-α-N-oxide (3) and (+)-N-methylnandigerine-β-N-oxide (4) were isolated from the leaves of Polyalthia longifolia (Sonn.) Thwaites (Annonaceae).
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■ Synthesis of (±)-(2R*,11bS*)-3’-Aryl-9,10-dimethoxy-1,3,4,5,7,11b-hexahydrospiro[benzo[a]quinolizin-2,5’-oxazolidine]-2’,4’-diones
J. Carlos Menéndez, Carmen Avendaño, and Mónica M. Söllhuber*
*Departamento de Química Orgánica y Farmacéutica, Facultad de Farmacia, Universidad Complutense de Madrid, Ciudad Universitaria, 28040 Madrid, Spain
Abstract
The synthesis of (±)-(2R*,11bS*)-3’-aryl-9,10-dimethoxy-1,3,4,6,7,11b-hexahydrospiro[benzo[α] quinolizin-2,5’-oxazolidine]-2’,4’-diones (1) was achieved by two alternative routes involving the treatment of cyanohydrin 3 with aryl isocyanates via 4-imino derivatives 5 and 6 or the cyclization of the hydroxy ester 9 with aryl isocyanates. Compounds 1 present a trans Conformation in the quinolizidine system and exist in a (2R*,11bS*) configuration.
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■ The Reaction of 2-Chiloro-10-N-methylphenothiazine with Aromatic Nitriles and Lithium Dialkylamides in THF: Synthesis Structure of 1-Cyano-2-(3’,4’,5’-trimethoxybenzyl)-10-N-methylphenothiazine
Edward R. Biehl,* Subhash P. Khanapure, Upali Siriwardane, and Matt Tschantz
*Department of Chemistry, Southern Methodist University, P.O. Box 750314, Dallas, TX 75275-0314, U.S.A.
Abstract
10-N-Methyl-1,2-didehydrophenothiazine (2), generated in situ from 10-N-methyl-2-chlorophenothiazine (1), reacts via the tandem addition-rearrangement aryne (TARA) mechanism with lilhio-arylacetonitriles yielding rearranged products (3a-c), after proton quench. The X-ray structure of title compound 3a demonstrates conclusively that the initial nitrile anion addition step in the TARA reaction occurs at the 2-position of 2. In previous studies of nucieophilic additions to 2, this regioselsctivity had only been assumed on the basis of the well-documented strong meta-directing effect of the lo-nitrogen atom.
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■ An Imprived Synthesis of 2-Carbamoyloxymethyl-1,4-dihydropyridine
Kunio Suzuki,* Ryosuke Ushijima, Tetsuji Myiano, and Susumu Nakagawa
*Okazaki Research Laboratories, Banyu Pharmaceutical Co., Ltd., 3-9-1, Kamimutuna, Okazaki, Aichi 444, Japan
Abstract
A new synthesis of 3-amino-4-carbamoyloxybutenoic esters by conjugate addition of ammonia to 4-carbamoyloxy-2-butynoic esters is reported. Numerous dihydropyridines were prepared from the resulting 3-aminobutenoates by condensation with benzylideneacetoacetates.
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■ Photochemistry of 5-(2-Acetoxyaryl)-2(3H)-furanones. 2. Isolation of Chromome-3-acetic Acids and Their Photodecarboxylation to 3-Methychromones
Luis Fillol, Roberto Martínez-Utrilla, Miguel A. Miranda,* and Isabel M. Morera
*Departamento de Química Oránica, Facultad de Farmacia, Av. Blasco Ibañez 13, 46010 Valencia, Spain
Abstract
Irradiation of the enol lactones 1a,b in methanol led to the vinyl ketones 2a,b and the chromones 3a,b, while irradiation in benzene gave the vinyl ketones 2a,b and the chromones 4a,b and 5a,b. The photodecarboxylatian of 4a,b to 5a,b, analogous to that of phisnylacetic acid, is very efficient. The mechanistic implications of these observations are discussed.
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■ Studies of the Chemical Constitutions of the Seeds of Peganum harmala; Isolation and Structure Elucidation of Two β-Carbolines — Harmalacine and Norharmine
Salimuzzaman Siddiqui,* Obaid Yusuf Khan, Shaheen Faizi, and Bina Shaheen Siddiqui
*H. E. J. Postgraduate Institute of Chemistry, University of Karachi, Karachi-75270, Pakistan
Abstract
A new tetracyclic β-carboline, harmalacinine, has been isolated from the seeds of Peganum harmala, along with norharmine, and their structures elucidated as I and II respectively through spectral studies.
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■ Studies in the Formation of Oxidoles from Their Indolozabicyclo[3.3.1]nonane Counterparts and Implications for the Biogenesis of Alstonisine
Sean P. Hollinshead, Desirée S. Grubisha, Dennis W. Bennett, and James M. Cook*
*Department of Chemistry, University of Wisconsin-Milwaukee, Milwaukee, Wisconsin 53201, U.S.A.
Abstract
Treatment of the Na-H indoloazabicyclo[3.3.1]nonane 5 with t-BuOCl and hydrolysis of the intermediate chloroindolenine provided the oxindole 6 in 88% yield. In contrast, Na-methyl analogues 9a-c failed to rearrange to the corresponding oxindoles when reacted under the analogous conditions. Instead, the indolooctane-1,4-dione 11 and an isomer related to 12 were isolated from the oxidation of 9a. The implications in regard to the biogenesis of alstonisine 2 are discussed.
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■ A Facile Synthesis of 2-Aryl- and 2-Heteroaryl-substituted 4-Aminoquinolines
Lucjan Strekowski,* Suk-Bin Kong, Marek T. Cegla, and Donald B. Harden
*Department of Chemistry, Georgia State University, University Plaza, Atlanta, GA 30303, U.S.A.
Abstract
Schiff’s bases, obtained from 2-aminobenzonitrile and aryl or heteroaryl methyl ketones, are lithiated with lithium diisopropylamide at the methyl group. The intermediate carbanions undergo cyciization to a quinoline system in a high yield. The corresponding Schiff’s base obtained from propiophenone undergoes an unusual addition reaction with the lithium reagent instead.
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■ Formation of Regioisomeric Tetrahydroisoxazolo[2,3-d][1,4]benzodiazepines by Kinetic and Thermodynamic Controls
Irina Merenda, Rosaria Ottanà, Giovanni Romeo,* and Enrico Rotondo
*Università di Messina, Viale Annunziata, 98168 Messina, Italy
Abstract
1,3-Dipolar cycloaddition of 1,4-benzodiazepine N-oxide with acrylic esters produces annelated 4- and 5-substituted isoxazolidines. 4-Substituted regioisomers are unstable at higher reaction temperatures and rearrange pIesumably via a 1,3-dipolar cycloreversion to regenerate 5-substituted derivatives. structure and stereochemistry of cycloadducts have been assigned by means of 1H nmr spectroscopy assisted by NOE measurements. The experienced regiochemistry has been rationalized according to the electron-rich nature of benzodiazepine nitrones.
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■ N-Substituted Pyridinium Salts
Wanda Sliwa* and Barbara Mianowska
*Institute of Chemistry and Environmental Protection, Pedagogical University, Al. Armii Krajowej 13/15, 42-201 Czestochowa, Poland
Abstract
N-Substituted pyridinium salts are presented in view of their syntheses, reactivity and physicochemical properties, along with their biological activities and applications.
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■ Heterocyclic Sonochemistry
Yu. Goldberg, R. Strukovich, and E. Lukevics*
*Latvian Institute of Organic Synthesis, Aizkraukles 21, Riga, LV-1006, Latvia
Abstract
Sonochemical reactions involving heterocyclic compounds are surveyed. Major synthetic applications of sonolysis in the chemistry of heterocyclic compounds are described.