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. 57, No. 3, 2002
Published online:
■ Nucleophilic Substitution Reaction on the Nitrogen of Indole Nucleus: A Novel Synthesis of 1-Aryltryptamines
Toshikatsu Hayashi, Wu Peng, Yu-ya Nakai, Koji Yamada, and Masanori Somei*
*Faculty of Pharmaceutical Sciences, Kanazawa University, 13-1 Takara-machi, Kanazawa 920-0934, Japan
Abstract
1-Hydroxytryptamine derivatives undergo nucleophilic substitution reaction on the indole nitrogen (Na) as a general reaction by the treatment with acid, providing a novel synthetic method for 1-aryltryptamines. Depending on the structures of nucleophiles, 5- and 7-substituted tryptamines can also be produced in addition to the 1-aryltryptamines.
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■ A New Approach to 6-Nitro-1H-[1,4]-diazepines
Nagatoshi Nishiwaki,* Takuma Ogihara, Mina Tamura, Noriko Asaka, Kazushige Hori, Yasuo Tohda, and Masahiro Ariga*
*Department of Chemistry, Osaka Kyoiku University, 4-698-1 Asahigaoka, Kashiwara, Osaka 582-8582, Japan
Abstract
2,3-Disubstituted 2,3-dihydro-6-nitro-1H-[1,4]-diazepines are prepared with easy experimental manipulations from formylated nitroenamine, which behaves as the synthetic equivalent of nitromalonaldehyde usable in organic media.
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■ Silver Ion-mediated Desulfurization of N,N-Disubstituted 2-Hydroxythiobenzamides
Isao Shibuya,* Kazumasa Honda, Yasuo Gama, and Masao Shimizu
*National Institute of Advanced Industrial Science and Technology, 1-1-1 Higashi, Tsukuba, Ibaraki 305-8565, Japan
Abstract
Silver ion–mediated desulfurization of N-(2- hydroxythiobenzoyl)morpholine (1a) or -piperidine (1b) was used to develop a new synthetic method for heterocycles such as 1,3-benzoxazin-1-ium salts. 2-Amino-4-morpholino- and 2-amino-4-piperidino-1,3-benzoxazin-1-ium perchlorate (2a, 2b) or 2-(N,N-dimethylamino)-4-morpholino- and 2-(N,N- dimethylamino)-4-piperidino-1,3-benzoxazin-1-ium perchlorate (3a, 3b) were obtained by treatment of 1a and 1b, respectively,with silver perchlorate in the presence of excess cyanamide or N,N-dimethylcyanamide, and the structure of 3a was confirmed by X-Ray crystallography. Desulfurization of 1 with AgOCN afforded 1,3-benzoxazin-2-ones (4). In addition, treatment of 1 with methyl cyanoacetate in the presence of silver trifluoroacetate and triethylamine gave 3-cyanochromen-2-ones (5).
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■ A Structural and Conformational Study of 8-p-Nitrocinnamyl-3-propionyl-3,8-diazabicyclo[3.2.1]octane, Selective Agonist of μ-Opioid Receptors
Roberto Artali, Daniela Barlocco, Gabriella Bombieri,* and Fiorella Meneghetti
*Instituto di Chimica Farmaceutica e Tossicologica, Universita di Milano, Viale Abruzzi, 42, 20131 Milano, Italy
Abstract
8-p-Nitrocinnamyl-3-propionyl-3,8-diazabicyclo[3.2.1]octane (2b) and its isomer (1b), having the nitrogen substituents exchanged, have been compared by X-Ray structural analysis. The different orientation of the cinnamyl chain in the two derivatives has been discussed and related to the pharmacological properties.
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■ Synthesis of New Atropisomers Derived from Methoxychloroacridine. Preparation of Enantiomerically Pure (aR)-(-)-2,2’-Dihydroxy-9,9’-biacridine
Anh Tuan Lormier, Gérard Boyer,* Robert Faure, and Jean Pierre Galy
*UMR 6009, Laboratoire de Valorisatin de la Chimie Fine, Case 552, Université Aix-Marseille III, Avenue Escadrille Normandie-Niemen, 13397 Marseille Cedex 20, France
Abstract
New biacridinyl atropisomers were obtained from symmetric ligand 2,2’-dihydroxy-9,9’-biacridine (4), prepared from 9-chloro-2-methoxyacridine. Alternative O-acylation and alkylation led to different polycycles and to a biacridinyl crown ether. The molecular structures of 2,2’-di(p-chlorobenzoyloxy)-9,9’-biacridinyl (5) and (9,9’-bisacridinyl)-2,2’-dihydroxy-bis-(camphanate) ester (13) were solved by X-Ray crystallography, showing a ‘scissor-like’ host conformation and guest inclusion of chloroform and acetonitrile. The determination of X-Ray structure of one diastereomer (13) allows to assign the absolute configuration of enantiomerically recovered (aR)-(-)-2,2’-dihydroxy-9,9’-biacridinyl.
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■ Practical Syntheses of 5-Trifluoromethyl-1H-indoles
Jean-Gilles Parmentier, Guillaume Poissonnet, and Solo Goldstein*
*Chemistry Research Division A, Institut de Recherches Servier, 11 rue des Moulineaux, 92150 Suresnes, France
Abstract
Short and convenient syntheses of 5-trifluoromethyltryptamine and 5-trifluoromethyltryptophole have been realized via a regioselective, palladium catalyzed, coupling/annulation method involving functionalized alkynes and 2-iodo-4-trifluoromethylaniline. A new and improved approach for the preparation of 5-trifluoromethyl-1H-indole is also described.
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■ New Cyclic Peptides from Citrus aurantium
Teruki Matsumoto, Noriko Tashiro, Koichi Nishimura, and Koichi Takeya*
*School of Pharmacy, Tokyo University of Pharmacy and Life Science, 1432-1 Horinouchi, Hachioji, Tokyo 192-0392, Japan
Abstract
Two new cyclic peptides were isolated from the fruit peels of Citrus aurantium. Their structures were elucidated as cyclo (-Gly-Leu-Val-Leu-Pro-Ser-) and cyclo (-Gly-Gly-Leu-Leu-Leu-Pro-Pro-Phe-) by intensive 2D NMR analysis and chemical evidence.
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■ Benzo-1,4-oxathiins and Benzo-1,4-dithiins from 4,5-Disubstituted 1,2,3-Thiadiazoles
Alan R. Katritzky,* George N. Nikonov, Dmytro O. Tymoshenko, Elizabeth L. Moyano, and Peter J. Steel
*Center for Heterocyclic Compounds, Department of Chemistry, University of Florida, P. O. Box 117200, Gainesville, FL 32611-7200, U.S.A.
Abstract
4-Aryl(or heteroaryl)-5-heterosubstituted 1,2,3-thiadiazoles on heating in the presence of sodium hydride undergo ring opening with nitrogen elimination followed by recyclization to form the corresponding 1,4-benzoxathiins and 1,4-benzodithiins.
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■ On the Reactions of 6-Phosphoranylideneaminouracils and Related 6-Aminouracils with 2,4,6-Cyclooctatrienone: Reactions of the Intermediates of Uracil-annulated 8-Azabicyclo[5,3,1]undecatetraene Ring Systems
Makoto Nitta* and Hiromi Kanda
*Department of Chemistry, School of Science and Engineering, Waseda University, 3-4-1 Okubo, Shinjuku-ku, Tokyo 169-8555, Japan
Abstract
The reaction of 1,3-dimethyl-6-phosphoranylideneaminouracil (4) with 2,4,6-cyclooctatrienone (7) in AcOH gives an intermediacy of uracil-annulated 8- azabicyclo[5.3.1]undeca-2,4,7,9-tetraene (9), which results in the formation of 9- acetoxy-5a,10-methano-2,4-dimethyl-2H-5,5a,6,8a,9,10-hexahydrocyclopent[b]-pyrimido[5,4-f]azepine-1,3(4H)-dione and 1,3,7- and 1,3,5-trimethylpyrido[2,3-d]pyrimidine-2(1H),4(3H)-diones (12 and 13) after several reaction sequences. A similar reaction using 6-amino-1,3-dimethyluracil (5) also afforded the same products probably via uracil-annulated 8-azabicyclo[5.3.1]undeca-2,4,6,9-tetraene (14). A similar intermediate is also postulated in the reaction of 3-methyl-6- methylaminouracil (6) with 2,4,6-cyclooctatrienone, and results in the formation of 9-acetoxy-5a,10-methano-2,4,5-trimethyl-2H-5,5a,6,8a,9,10-hexahydrocyclopent[b]pyrimido[5,4-f]azepine-1,3(4H)-dione (26), 3,7,8- and 3,5,8-trimethylpyrido[2,3-d]pyrimidine-2(3H),4(8H)-diones (27 and 28).
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■ Amino Acid-derived 4-Alkyl-4-carboxy-2-azetidinones. New Insights into β-Lactam Ring Formation and N-Deprotection
Guillermo Gerona-Navarro, Ma Angeles Bonache, Nuria Reyero, Ma Teresa García-López, and Rosario González-Muñiz*
*Centro de Química Orgánica 'Manuel Lora-Tamayo', Instituto de Química Médica, C. S. I. C., Calle Juan de Cierva, 3, 28006 Madrid, Spain
Abstract
The preparation and N-deprotection of a series of phenylalanine-derived 2-azetidinones incorporating 2,4-dimethoxybenzyl (Dmb), 2,3,4-, 2,4,6- and 3,4,5-trimethoxybenzyl (Tmb) groups at 1 position are described. The base-promoted cyclization of the corresponding methoxy-substituted Nα-benzyl-Nα-chloroacetyl derivatives to the 1,4,4-trisubstituted azetidinones proceeded with moderate to good yields, except for the 2,4,6-Tmb analogue. In spite of the number and position of the OMe groups, N-unsubstituted β-lactams were obtained by oxidative debenzylation using potassium peroxodisulfate. Alternatively, debenzylation of Pmb, Dmb and Tmb 2-azetidinones with TFA/anisole resulted in concomitant β-lactam opening to α-benzylaspartic acid derivatives.
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■ Design and Synthesis of a Novel Cyclophane as Host for Aryl Phosphate
Muneharu Miyake* and Craig S. Wilcox
*College of Pharmacy, Nihon University, 7-7-1 Narashinodai, Funabashi-shi, Chiba 274-8555, Japan
Abstract
A novel Tröger base derived cyclophane bearing mercaptoimidazole groups on the alkyl chains as blanches of 6H,12H-5,11-methanodibenzo[b,f][1,5]diazocine skeleton was synthesized in order to investigate the ability as macrocyclic enzyme models to incorporate phosphotyrosine in future.
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■ Synthesis and Structural Assignment of Functionalized 8,9-Diazatricyclo[4.4.0.01,5]decane: A New Tricyclic System Including the Pyridazine Ring
Xavier Cachet, Brigitte Deguin, François Tillequin,* Michel Koch, and Angèle Chiaroni
*Laboratoire de Pharmacognosie,UMR 8638 associee au CNRS, Faculté des Sciences Pharmaceutiques et Biologiques, Université René Descartes, 4, Avenue de l'Observatoire, 75270 Paris Cedex, France
Abstract
Reaction of hydrazine hydrate with the dipivaloyl ester of (1S, 4R, 5R, 6R)-4-hydroxy-2-hydroxymethyl-1-formylbicyclo[3.1.0]hex-2-ene-6-carboxylic acid (2) afforded (1S, 2R, 4R, 5R, 6R)-8,9-diaza-2-[(2,2-dimethylpropanoyloxy)methyl]-7-oxotricyclo[4.4.0.01,5]dec-9-en-4-yl 2,2-dimethylpropanoate (3). The structure and conformation of the new 8,9-diazatricyclo[4.4.0.01,5]dec-9-ene system were determined by X-Ray cristallography and 2D NMR experiments.
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■ The Sesquiterpenoid from Polyalthia cheliensis Hu
Wei Ming Zhu, Shun Lin Li, Yue Mao Shen, Xian Jiang Ning, Bi Tao Zhao, and Xiao Jiang Hao*
*Laboratory of Phytochemistry, Kunming Institute of Botany, The Chinese Academy of Sciences, Kunming, Yunnan 650204, China
Abstract
From the dried leaves of Polyalthia cheliensis Hu, three sesquiterpenoids were isolated. Their structures of the new sesquterpene, 3’’,3’’’- bispolycerasoidol (1) was elucidated by spectroscopic and chemical methods.
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■ Survey of Briarane-Type Diterpenoids of Marine Origin
Ping-Jyun Sung,* Jyh-Horng Sheu, and Jun-Ping Xu
*National Museum of Marine Biology and Aquarium, 2 Houwan Road, Checheng, Pingtung, Taiwan 944, Taiwan, R.O.C.
Abstract
The structures, names, biological activities, and references of two hundred ninety-nine marine original briarane-type metabolites are described and compiled in tabular form in this review. All briarane-type natural products are obtained from marine invertebrates, including various octocorals, a nudibranch, and a sponge. Some of these compounds showed potential biological activities.