Regular Issue

Vol. 57, No. 3, 2002

14 data found. 1 - 14 listed
Communication | Regular issue | Vol 57, No. 3, 2002, pp. 421 - 424
Published online:
DOI: 10.3987/COM-01-9417
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


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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Communication | Regular issue | Vol 57, No. 3, 2002, pp. 425 - 428
Published online:
DOI: 10.3987/COM-02-9438
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


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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Paper | Regular issue | Vol 57, No. 3, 2002, pp. 429 - 437
Published online:
DOI: 10.3987/COM-01-9396
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


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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Paper | Regular issue | Vol 57, No. 3, 2002, pp. 439 - 447
Published online:
DOI: 10.3987/COM-01-9398
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


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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Paper | Regular issue | Vol 57, No. 3, 2002, pp. 449 - 463
Published online:
DOI: 10.3987/COM-01-9408
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


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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Paper | Regular issue | Vol 57, No. 3, 2002, pp. 465 - 476
Published online:
DOI: 10.3987/COM-01-9411
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


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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Paper | Regular issue | Vol 57, No. 3, 2002, pp. 477 - 482
Published online:
DOI: 10.3987/COM-01-9419
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


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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Paper | Regular issue | Vol 57, No. 3, 2002, pp. 483 - 489
Published online:
DOI: 10.3987/COM-01-9422
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.


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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Paper | Regular issue | Vol 57, No. 3, 2002, pp. 491 - 499
Published online:
DOI: 10.3987/COM-01-9425
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


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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Note | Regular issue | Vol 57, No. 3, 2002, pp. 501 - 513
Published online:
DOI: 10.3987/COM-01-9400
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


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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Note | Regular issue | Vol 57, No. 3, 2002, pp. 515 - 522
Published online:
DOI: 10.3987/COM-01-9409
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


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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Note | Regular issue | Vol 57, No. 3, 2002, pp. 523 - 528
Published online:
DOI: 10.3987/COM-01-9427
Synthesis and Structural Assignment of Functionalized 8,9-Diazatricyclo[,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


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[,5]dec-9-en-4-yl 2,2-dimethylpropanoate (3). The structure and conformation of the new 8,9-diazatricyclo[,5]dec-9-ene system were determined by X-Ray cristallography and 2D NMR experiments.

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Note | Regular issue | Vol 57, No. 3, 2002, pp. 529 - 534
Published online:
DOI: 10.3987/COM-02-9435
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


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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Review | Regular issue | Vol 57, No. 3, 2002, pp. 535 - 579
Published online:
DOI: 10.3987/REV-01-546
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.


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.

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14 data found. 1 - 14 listed