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. 43, No. 2, 1996
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■ Efficient Mononitration of Indolic Compounds with Nitric Acid Impregnated on Silica Gel
Nathalie Roué, Thierry Delahaigue, and Roland Barret*
*Université de Champagne-Ardenne, UFR de Pharmacie, Laboratoire d'Isolement, Transformation et Synthèse de Substances Naturelles, associé au CNRS, 51 rue Cognacq-Jay-F 51096 Reims Cedex, France
Abstract
The methoxyindoles (N-benzenesulfonyl and 2-carbomethoxy) were mononitrated with nitric acid adsorbed on silica gel under mild conditions to give mononitroindoles in good chemical yields.
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■ Stereoselective Intramolecular Michael Reaction of the 18-Membered α,β-Unsaturated Macrolactam: MM2 Transition Structure Models
Haruo Yamada, Takashi Takahashi*, Yutaka Kanda, Yutaka Saitoh, and Tohru Fukuyama
*Department of Chemical Engineering, Tokyo Institute of Technology, Meguro, Tokyo 152, Japan
Abstract
Intramolecular Michael reaction of the 18-membered α,β-unsaturated lactam, a key reaction in the total synthesis of leinamycin (1), and a discussion of its high diastereoselectivity based on MM2 transition structure models are presented.
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■ Asymmetric Syntheses of (-)-Erinapyrones A and B
Yoshihiro Noda,* Takeshi Fukaya, and Mitsuko Kikuchi
*Department of Industrial Chemistry, College of Engineering, Nihon University, Tamura-machi, Koriyama, Fukushima 963, Japan
Abstract
(-)-Erinapyrone A and (-)-erinapyrone B have been synthesized in short steps from bis-2-(1,3-dithianyl)methane, (S)-propylene oxide and (R)-benzyl glycidyl ether. These synthetic compounds, however, showed higher specific rotation values than those of the natural products. Both enantiomers of erinapyrones A and B were synthesized by the use of antipodal epoxides. These enantiomers showed same specific rotation values with reverse signs. The racemic compounds were also synthesized as standard samples for analysis on chiral gc column for optical resolution.
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■ Total Synthesis of 8-(1,1-Dimethylallyl)apigenin
Hélène Raguenet, Denis Barron,* and Anne-Marie Mariotte
*Pharmacognosy Laboratory, School of Pharmacy, Joseph-Fourier University-Grenoble I, 38706 La Tronche Cedex, France
Abstract
8-(1,1-Dimethylallyl)apigenin has been synthesized in 5 steps from 2’,4’-dibenzylphloroacetophenone and 4-O-methoxyethoxymethylbenzaldehyde. The strategy involved protection of the 4’-hydroxyl in apigenin by a methoxyethoxymethyl group, followed by specific O-prenylation at position 7. Claisen rearrangement of the 7-prenyl-4’-methoxyethoxymethylapigenin performed in one step both the 1,1-dimethylallylation at position 8, and removal of the 4’-methoxyetoxymethyl protecting group.
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■ Synthesis, Conformation Analysis and Biological Evaluation of 2-(2,3-Dideoxy-β-D-ribofuranosyl)pyridine-4-carboxamide
Pieter E. Joos,* Eddy L. Esmans, Frank C. Alderweireldt, André De Bruyn, Jan Balzarini, and Erik De Clercq
*University of Antwerp (RUCA), Department of Chemistry, Groenenborgerlaan 171, B-2020-Antwerp, Belgium
Abstract
2-(2,3-Dideoxy-β-D-ribofuranosyl)pyridine-4-carboxamide (2) was synthesized starting from the protected sugar analogue (3). Coupling of this compound with 2-lithio-4-(4,5-dihydro-4,4-dimethyloxazol-2-yl)pyridine (4), subsequent mesylation, reduction, deprotection and ammonolysis gave (2) as an anomeric mixture. α/β-Separation was done by semi preparative hplc on a Lichrosorb 10 RP 8 colum. In addition 2D-NOESY nmr spectroscopy was used for the assignment of the α/β-anomers of (2). High resolution 1H nmr allowed us to do a conformation analysis of compound (β-2). Finally the β-anomer of (2) was evaluated for its biological activity.
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■ Novel Rearrangement of cis-N-Alkyl-3-phenylaziridin-2-yl Phenyl Ketone Tosylhydrazones with Ethlyl Ether-Boron Trifluoride. Preparation of 1,2,5,6-Tetrahydro-1,2,3-triazine Derivatives
Motonobu Morioka, Masahiko Kato, Hiroshi Yoshida, and Tsuyoshi Ogata*
*Department of Applied Chemistry, Faculty of Engineering, Shizuoka University, Hamamatsu-shi 432, Japan
Abstract
1-Alkyl-4,6-diphenyl-1,2,5,6-tetrahydro-2-tosyl-1,2,3-triazine derivatives (8a-g, i-k) which had a new skeletal ring were obtained in moderate yield (77-49 %) by the rearrangement of cis-N-alkyl-3-phenylaziridin-2-yl phenyl ketone tosylhydrazones (3a-g, i-k) with ethyl ether-boron trifluoride (1/1) (7) in chloroform under room temperature. The starting materials (3a-l) were prepared in good yield (88-39%) by the condensation of cis-N-alkyl-3-phenylaziridin-2-yl phenyl ketones (1a-l) with tosylhydrazine (2) in chloroform in the presence of PPE (polyphosphoric acid ethyl ester) hydrolysate as a catalyst.
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■ Synthesis of Theophylline Nucleosides from 6-Amino-1,3-dimethyl-5-N-glycosylideneiminouracil
Rodrigo Rico Gómez* and Josefa Ríos Ruiz
*Departamento de Química Orgánica, Facultad de Ciencias, Universidad de Málaga, 29071 Málaga, Spain
Abstract
A new synthesis for 7-glycosyl-theophylline from 6-amino-1,3-dimethyl-5-N-D-glycosylideneiminouracil and diethoxymethyl acetate is proposed. The structures of obtained theophylline nucleosides are described.
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■ A Fischer-Indole Approach to Pyrrolo[2,3-d]pyrimidines
Edward C. Taylor and Baihua Hu
*Department of Chemistry, Princeton University, Princeton, New Jersey 08544, U.S.A.
Abstract
Several new 5,6-disubstituted pyrrolo[2,3-d]pyrimidines have been prepared by thermolysis of ketone hydrazones of 2-amino-6-hydrazino-4(3H)-oxopyrimidine (8) (the Fischer-Indole Synthesis).
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■ Photolysis of 3-Bromochroman-4-ones
M. Consuelo Jiménez, Miguel A. Miranda*, and Rosa Tormos
*Departamento de Química/ Instituto de Tecnología Química, UPV-CSIC, Universidad Politécnica de Valencia, Apartado 22012, E-46071-Valencia, Spain
Abstract
Photolysis of 3-bromochroman-4-ones (1a-f) leads to debrominated chromanones (2a-f) and chromones (3a-f) as major products. Their formation is accounted for in terms of primary cleavage of the carbon halogen bond to give α-carbonyl radicals (I) and/or cations (II). In the case of the 2,2-disubstituted compounds (1d-f), intermediates (II) undergo rearrangement with 1,2-shift of the phenyl or benzyl substituent prior to deprotonation. Minor by-products are the pentacyclic pyrone (4e) or 2-methylchromone (3a) (starting from 1e and 1f, respectively).
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■ Synthesis of Thieno[2,3-d]pyrimidine Analogues of the Potent Antitumor Agent N-{4-[2-(2-Amino-4(3H)-oxo-7H-pyrrolo[2,3-d]pyrimidin-5-yl)ethyl]benzoyl}-L-glutamic Acid (LY231514)
Edward C. Taylor ,* Hemantkumar H. Patel, Gowravaram Sabitha, and Rajendra Chaudhari
*Department of Chemistry, Princeton University, Princeton, NJ 08544, U.S.A.
Abstract
Several thieno[2,3-d]pyrimidine analogues of the potent antitumor agent N-{4-[2-(2-amino-4(3H)-oxo-7H-pyrrolo[2,3-d]pyrimidin-5-yl)ethyl]benzoyl}-L-glutamic acid (LY231514,7) have been prepared by two different strategies. The first involved S-alkylation of the 6-mercaptopyrimidines (13) and (14) with the α-haloketone (12), followed by cyclization to the thienopyrimidines (17) and (18) respectively. The second involved synthesis of the 2-amino-3-carbomethoxy- and 2-amino-3-cyano-thiophenes (19) and (20) which wre cyclized with acetonitrile to the corresponding thienopyrimidines (21) and (22). Compounds (17, 18, 21, and 22) were hydrolyzed to the acids which were coupled with dimethyl L-glutamate, and the resulting monopeptide esters were saponified to the target analogs.
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■ Behavior of Oxotetrahydrobenzo[b]- and [c]thiophenes and Their α-Hydroxymethylene Derivatives in the Fischer Indole Synthesis
Laurent Martarello, Delphine Joseph, and Gilbert Kirsch*
*Laboratoire de Chimie Organique, Université de Metz, Ile du Saulcy, F-57045 Metz cedex, France
Abstract
We described an approach to thienocarbazoles via a Fischer indole synthesis starting directly from oxotetrahydrobenzo[b]- and [c]thiophenes or from their α-hydroxymethylene derivatives with a Japp-Klingemann reaction to make the hydrazones which are cyclised under acidic conditions.
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■ Synthesis of 6-Acyl-2, 2-dimethyl-2-silatetralins
Osamu Hoshino*, Akihisa Hirokawa, Atsuhiro Tatsuno, Ayako Kigoshi, Harumi Watahiki, and Teruo Kurihara
*Faculty of Pharmaceutical Sciences, Science University of Tokyo, 12, Ichigaya Funagawara-machi, Shinjuku-ku, Tokyo 162, Japan
Abstract
Friedel-Crafts reaction of 2-silatetralin (4) with acid anhydrides (acetic anhydride, succinic anhydride, glutaric anhydride, phthalic anhydride, cis-1, 2-cyclohexanedicarboxylic anhydride, and diphenic anhydride) or benzoyl chloride in the presence of AlCl3 in CH2Cl2 at room temperature gave exclusively the corresponding 6-acyl-2-silatetralins in fair to good yield. This findings were supported by the MNDO molecular orbital calculations of 2-silatetralin (4).
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■ A Synthesis of Fused Pyrimidine Mono-N-oxides
Stanislaw Ostrowski
*Institute of Organic Chemistry, Polish Academy of Sciences, ul. Kasprzaka 44/52, PL 01-224 Warszawa, Poland
Abstract
An efficient synthesis of functionalized fused pyrimidine mono-N-oxide derivatives from the nitroaromatic compounds (involving the Vicarious Nucleophilic Substitution of Hydrogen and cyclocondensation of aromatic orthoaminooximes with orthoesters) is described.
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■ New Derivatives of Pyrroline N-Oxides as Spin Traps
Prabhat Arya
*Steacie Institute for Molecular Sciences, National Research Council of Canada, Ottawa, Ontario, K1A 0R6, Canada
Abstract
Pyrroline-N-oxides containing maleimido (4), biotin (5a) and ether side chain (6 and 7) at the C-4 position have been synthesized starting from a common synthon (8).
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■ New Cassane Diterpenes from Caesalpinia bonduc (Fabaceae)
Takeshi Kinoshita,* Michiko Kaneko, Hiroshi Noguchi, and Isao Kitagawa
*Faculty of Pharmaceutical Sciences, Teikyo University, 1091-1 Suarashi, Sagamiko-machi, Tsukui-gun, Kanagawa 199-01, Japan
Abstract
New cassane diterpenes, neocaesalpins A and B, were isolated from the seeds of Caesalpinia bonduc (Fabaceae) and their stuructures were deduced on the basis of the spectroscopic evidence. These compounds are characterized as having an α,β-butenolide moiety whereas caesalpins, a group of diterpenes previously known from the same plant and related species, possess the furan ring. The possible biogenetic scheme for formation of an α,β-butenolide was postulated as the furan ring undergoing peroxidation followed by isomerization to give rise to the hemiketal lactone.
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■ Practical Synthesis of (R)-1-Benzyl-3-hydroxy-2,5-pyrrolidinedione and Its Acetate from L-Tartaric Acid
Hiroshi Tomori, Hiroshi Maruyama, and Katsuyuki Ogura*
*Department of Applied Chemistry, Faculty of Engineering, Chiba University, 1-33 Yayoicho, Inage-ku, Chiba 263, Japan
Abstract
An efficient method for preparing (R)-1-benzyl-3-hydroxy-2,5-pyrrolidinedione and its acetate is described starting from L-tartaric acid, which affords the desired compounds with 99% ee in good overall yields (63-74%).
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■ Components of the Root Bark of Morus cathayana. 1. Structures of Five New Isoprenylated Flavonoids, Sanggenols A - E and a Diprenyl-2-arylbenzofuran, Mulberrofuran V
Toshio Fukai, Yue-Hu Pei, Taro Nomura,* Chun-Quan Xu, Li-Jun Wu, and Ying-Jie Chen
*Faculty of Pharmaceutical Sciences, Toho University, 2-2-1 Miyama, Funabashi, Chiba 274, Japan
Abstract
Five new isoprenylated flavonoids, sanggenols A (1), B (2), C (3), D (4), and E (5), along with a diprenyl-2-arylbenzofuran, mulberrofuran V (6), were isolated from the Chinese moraceous plant, Morus cathayana. The structures of sanggenols A - E, and mulberrofuran V were shown to be 1 - 5 and 6, respectively, on the basis of spectroscopic evidence. Furthermore fourteen kinds of known phenolic compounds were also isolated.
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■ Synthesis of 7-Aryl-2-dimethylamino-3,4,5,6-tetrahydropteridine-4,6-diones
Edward C. Taylor,* Masahiko Takahashi,* and Norio Kobayashi
*Department of Materials Science, Faculty of Engineering, Ibaraki University, Hitachi, Ibaraki 316, Japan
Abstract
6-Amino-2-dimethylamino-5-nitrosopyrimidin-4(3H)-one (1) was condensed with a series of dimethylphenacylsulfonium bromides (2) in pyridine to yield 7-aryl-2-dimethylamino-3,4,5,6-tetrahydropteridine-4,6-diones (xanthopterin derivatives) (5) which were reduced to yield the corresponding 7,8-dihydro derivatives (6).
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■ Short Synthesis of 14,15-Didehydro-E-deplancheine, Presumed Biosynthetic Intermediate in the Formation from Geissoschizine, of Corynanthé Alkaloids Missing the Three-Carbon Unit at C-15
Mauri Lounasmaa,* Pirjo Hanhinen, and Reija Jokela
*Laboratory for Organic and Bioorganic Chemistry, Technical University of Helsinki, FIN-02150 Espoo, Finland
Abstract
A short synthesis of 14,15-didehydro-E-deplancheine (4) and its Z-analogue (5) is described.
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■ Approach to the Synthesis of 1,5-Diazaanthraquinones by Diels-Alder Reactions of Quinoline-5,8-diones
Ricardo A. Tapia,* Carmina Quintanar, and Jaime A. Valderrama
*Facultad de Química, Pontificia Universidad Católica de Chile, Casilla 306, Santiago-22, Chile
Abstract
9-Hydroxy- and 6-hydroxybenzo[g]quinoline-5,10-dione (18) and (22) have been obtained through the selective Diels-Alder reaction of 1-trimethylsilyloxy-1,3-butadiene (8) with quinoline-5,8-dione (2) and tetrahydroquinoline-5,8-dione (7) respectively. The treatment of quinone (2) with 1-dimethylamino-1-aza-1,3-butadiene (9) affords a mixture of the diazaanthraquinones (23) and (24) in a 1:3.6 ratio. The synthesis of 1,5-diazaanthraquinone (26) via the reaction of quinone (7) with azadiene (9) is also described.
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■ The Regioselective Photoinduced Aroylation at the 3-Position of Pyrrole Derivatives
Kazuaki Oda,* Rin Hiratsuka, and Minoru Machida
*Faculty of Pharmaceutical Sciences, Health Sciences University of Hokkaido, Ishikari-Tobetsu, Hokkaido 061-02, Japan
Abstract
Irradiation of arenecarbothioamide with pyrrole or indole derivatives gave regioselectively 3-aroylpyrrole or -indole derivatives, respectively.
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■ Studies on Isocyanides. 2-Isocyanothioanisole, a Synthetic Equivalent of the Benzothiazol-2-yl Anion
Ricardo Bossio, Stefano Marcaccini,* Roberto Pepino, and Tomás Torroba
*CNR, Centro di Studio sulla Chimica e la Struttura dei Composti Eterociclici e loro Applicazioni, Dipartimento di Chimica Organica "Ugo Schiff", Università di Firenze, via Gino Capponi 9, I-50121 Firenze, Italy
Abstract
A synthesis of 2-isocyanothioanisole (3) is described. The reaction between 3 and electrophilic reagents took place easily to give 2-functionalized benzothiazoles (6).