Regular Issue

Vol. 68, No. 12, 2006

20 data found. 1 - 20 listed
Communication | Regular issue | Vol 68, No. 12, 2006, pp. 2465 - 2469
Published online: 27th October, 2006
DOI: 10.3987/COM-06-10889
Synthesis of Octahydropyrrolo[3,2-c]pyridine Derivatives by the Catalytic Asymmetric Intramolecular Cycloaddition of Azomethine Ylides

Yoji Oderaotoshi,* Hiroyuki Miyata, Satoshi Minakata, and Mitsuo Komatsu*

*Department of Applied Chemistry, Graduate School of Engineering, Osaka University, 2-1 Yamadaoka, Suita, Osaka 560-0871, Japan


The synthesis of optically active octahydropyrrolo[3,2-c]pyridine derivatives was achieved via the asymmetric intramolecular cycloaddition of azomethine ylides using copper-bisphosphine complexes. Cu(OTf)2-(R,R)-CHIRAPHOS is a suitable catalyst for the reactions.

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Communication | Regular issue | Vol 68, No. 12, 2006, pp. 2471 - 2476
Published online: 2nd November, 2006
DOI: 10.3987/COM-06-10891
Synthesis of Chiral Non Racemic Indolizidin-3-ones as Peptidomimetic Scaffold

Delphine Halie, Joëlle Pérard-Viret, and Jacques Royer*

*Faculty of Pharmacy, UMR 8638 (CNRS-University Paris 5), 4 Avenue de l’Observatoire, 75270 Paris Cedex 06, France


A new asymmetric strategy has been devised to attain indolizidin-3-ones wich can be used as peptidomimetic scaffolds. The sequence is a two-step synthesis.

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Communication | Regular issue | Vol 68, No. 12, 2006, pp. 2477 - 2482
Published online: 2nd November, 2006
DOI: 10.3987/COM-06-10894
Sugar Binding to an Calix[4]arene-Based Receptor

Takeharu Haino,* Masaki Nakamura, and Yoshimasa Fukazawa*

*Department of Chemistry, Graduate School of Science, Hiroshima University, 1-3-1 Kagamiyama, Higashi-hiroshima, Hiroshima 739-8526, Japan


The binding properties of the calix[4]arene-based artificial receptor (1) toward carboxylate-containing sugars in DMSO are demonstrated. The receptor shows the 1:1 host-guest complexation with the sugars. The hydrogen bonds forming to the hydroxyl groups play a crucial role for the guest selection.

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Paper | Regular issue | Vol 68, No. 12, 2006, pp. 2483 - 2498
Published online: 24th October, 2006
DOI: 10.3987/COM-06-10862
Synthetic Utilization of Polynitro Aromatic Compounds. 5. Multi-Centered Reactivity Pattern in Reactions of 4,6-Dinitro-1,2-benzisothiazoles and -isothiazol-3(2H)-ones with C-, N-, O-, S-, and F-Nucleophiles

Sergei G. Zlotin,* Pavel G. Kislitsin, Fedor A. Kucherov, Evgeny A. Serebryakov, Yury A. Strelenko, and Andrei A. Gakh*

*Oak Ridge Naitonal Laboratory, 1 Bethel Valley Rd., Oak Ridge, TN 37831-6242, U.S.A.


Reactions of 4,6-dinitro-1,2-benzisothiazoles, -isothiazol-3(2H)-ones, and -isothiazol-3(2H)-one-1-oxides with C-, N-, O-, S-, and F-nucleophiles give products of aromatic nucleophilic substitution of one or two nitro groups, “vicarious” substitution of the hydrogen atom H-7, or heterocyclic S-N bond cleavage depending on the structure of the starting compound and the nature of the nucleophile. These reactions provide a new synthetic approach to a family of biologically active benzisothiazol-3(2H)-ones based on 2,4,6-trinitrotoluene (TNT).

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Paper | Regular issue | Vol 68, No. 12, 2006, pp. 2499 - 2507
Published online: 24th October, 2006
DOI: 10.3987/COM-06-10866
Crystal Structure of Triphenyl Cyamelurate (2,5,8-Triphenoxy-1,3,4,6,7,9,9b-heptaazaphenalene)

Marcus R. Schwarz, Helmut Ehrenberg, Matthäus A. Kloc, and Edwin Kroke*

*Institute for Inorganic Chemistry, TU-Bergakademie Freiberg, Leipziger Strasse 29, D-09596, Germany


2,5,8-Triphenoxy-1,3,4,6,7,9,9b-heptaazaphenalene (triphenyl cyamelurate, C6N7(OPh)3) was synthesized under solvent free conditions from cyameluric chloride (C6N7Cl3) and phenol via nucleophilic substitution. Needle-shaped crystals were obtained via a vapor transport method. Single crystal XRD revealed that C6N7(OPh)3 crystallizes in the monoclinic space group P 21/c with the lattice parameters a = 14.463(17) Å, b = 4.697(3) Å, c = 31.60(4) Å and β = 99.76(9)°. All three phenyl rings are rotated and inclined differently with respect to the central heptazine units, which themselves form inclined stacks along the b axis. Intermolecular cohesion is provided via dipolar, aromatic and van-der-Waals interactions as well as some weak C-H···N and C-H···O hydrogen bridges.

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Paper | Regular issue | Vol 68, No. 12, 2006, pp. 2509 - 2514
Published online: 31st October, 2006
DOI: 10.3987/COM-06-10875
Total Inversion of Cis-C5 Maxacalcitol into Its Trans-C5 Isomer via the Sulforene Intermediate

Tsuyoshi Yamauchi,* Koji Suzuki, Hitoshi Shimizu, and Masahiro Kato

*Pre-Clinical Research Department I, Fuji-gotemba Research Laboratories, Chugai Pharmaceutical Company, Ltd., 135, 1-Chome Komakado, Gotemba City, Shizuoka 412-8513, Japan


Total inversion of the cis-C5 configuration of Maxacalcitol, the unnatural 22-oxa-vitamin D3 analogue used for the treatment of secondary hyperparathyroidism and psoriasis, into the trans-C5 isomer has been accomplished stereoselectively via a formation of the sulforene intermediate for biological evaluation.

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Paper | Regular issue | Vol 68, No. 12, 2006, pp. 2515 - 2525
Published online: 24th October, 2006
DOI: 10.3987/COM-06-10877
Recyclization of 7-Fluoroalkyl-4,7-dihydroazolo[5,1-c]triazines into 5-(Pyrazolinylhydrazono)azoles in the Reactions with Hydrazides and Thiosemicarbazide

Olga G. Khudina, Evgeny V. Shchegol’kov, Yanina V. Burgart, Mikhail I. Kodess, Victor I. Saloutin,* and Oleg N. Chupakhin

*Institute of Organic Synthesis, Urals Branch, Russian Academy of Sciences, 20, S. Kovalevskaya st., Ekaterinburg, GSP-147, 620219, Russia


7-Fluoroalkyl-4,7-dihydroazolo[5,1-c][1,2,4]triazines react with hydrazides and thiosemicarbazide to form 5-(5-hydroxy-5-polyfluoroalkyl-2-pyrazoline-4-ylhydrazono)azoles as a result of triazine ring opening at bond C-7-N-8 and followed by regio-selective condensation.

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Paper | Regular issue | Vol 68, No. 12, 2006, pp. 2527 - 2547
Published online: 27th October, 2006
DOI: 10.3987/COM-06-10878
Hydantoins and Thiohydantoins Derived from 1,2,3,4-Tetrahydroisoquinoline-3-carboxylic Acid

Petr Jansa, Vladimír Wsól, Valerio Bertolasi, and Vladimír Machácek*

*Department of Organic Chemistry, Faculty of Chemical Technology, University of Pardubice, 53210 Pardubice, Czech Republic


The reaction of methyl (S)-1,2,3,4-tetrahydroisoquinoline-3-carboxylate with isocyanates (phenyl, naphthalen-1-yl, cyclohexyl, (S)-1-methylbenzyl) in ether has been used to prepare N-substituted methyl (3S)-2-aminocarbonyl-1,2,3,4-tetrahydroisoquinoline-3-carboxylates. These compounds were cyclised by action of CF3COOH to give the corresponding 2-substituted (10aS)-10,10a-dihydroimidazo[1,5-b]isoquinoline-1,3(2H,5H)-diones (hydantoins Tic-H). Hydantoins Tic-H were also prepared by the reaction of methyl (S)-1,2,3,4-tetrahydroisoquinoline-3-carboxylate with isocyanates (methyl, (1S)-1-methylbenzyl, 4-methylphenyl, 3-methylphenyl, 4-chlorophenyl, 2,4-dichlorophenyl, 4-methoxyphenyl, 5-chloro-2-methoxyphenyl, 3-chloro-4-ethoxyphenyl) and triethylamine in CH2Cl2. 2-Substituted (10aS)-3-thioxo-1,2,3,5,10,10a-hexahydroimidazo[1,5-b]isoquinolin-1-ones (thiohydantoins Tic-TH) were prepared analogously by the reaction of methyl (S)-1,2,3,4-tetrahydroisoquinoline-3-carboxylate with isothiocyanates (methyl, ethyl, allyl, phenyl). The optical purity of selected substances was determined chromatographically.

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Paper | Regular issue | Vol 68, No. 12, 2006, pp. 2549 - 2561
Published online: 31st October, 2006
DOI: 10.3987/COM-06-10879
Thermolysis of 5-Azido-4-arylpyridazin-3(2H)-ones: An Efficient and Versatile Synthesis of Pyridazino[4,5-b]indoles

Norbert Haider* and Andrea Wobus

*Department of Drug Synthesis, Faculty of Life Sciences, University of Vienna, Althanstrasse 14, A-1090 Vienna, Austria


5-Azido-4-arylpyridazin-3(2H)-ones, which are easily available from 4,5-dihalopyridazin-3(2H)-ones in few steps, were found to undergo in high yields a thermally induced cyclization into pyridazino[4,5-b]indole derivatives (“aza-carbolinones”) by formation of the N-5/C-5a bond via a nitrene insertion process. This new method is complementary to a previously reported pathway in which the C-4a/N-5 bond of the ring system is formed.

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Paper | Regular issue | Vol 68, No. 12, 2006, pp. 2563 - 2570
Published online: 27th October, 2006
DOI: 10.3987/COM-06-10881
Electrooxidative Cyclization of Hydroquinolyl Alcohols

Mitsuhiro Okimoto,* Takashi Yoshida, Masayuki Hoshi, Kazuyuki Hattori, Masashi Komata, Kaori Numata, and Kenta Tomozawa

*Department of Applied and Environmental Chemistry, Kitami Institute of Technology, Koen-cho 165, Kitami, Hokkaido 090-8507, Japan


Several hydroquinolyl, hydroisoquinolyl, and indolinyl alcohols were electrochemically oxidized in methanol in the presence of sodium methoxide and potassium iodide. The hydroquinolyl and hydroisoquinolyl alcohols afforded the corresponding intramolecular cyclization products through the bond formation between the α-carbon of the nitrogen atom and the oxygen atom of the hydroxy group. In contrast, the indolinyl alcohols underwent dehydrogenation to give the corresponding indolyl alcohols. Presumably, in all cases, the electrooxidation involves a two-electron oxidation process.

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Paper | Regular issue | Vol 68, No. 12, 2006, pp. 2571 - 2578
Published online: 2nd November, 2006
DOI: 10.3987/COM-06-10883
Synthesis of Chiral 1,2-Dihydropyridines and 2,3,4-Trisubstituted Pyridines from α-Amino Acids

Daiki Monguchi, Swapan Majumdar, and Takeo Kawabata*

*Institute for Chemical Research, Kyoto University, Uji, Kyoto 611-0011, Japan


Chiral 1,2-dihydropyridines were prepared by Dieckmann condensation of α-amino acid derivatives. The dihydropyridines were converted to 2,3,4-trisubstituted pyridines.

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Paper | Regular issue | Vol 68, No. 12, 2006, pp. 2579 - 2585
Published online: 27th October, 2006
DOI: 10.3987/COM-06-10885
First Synthesis of Trans- and Cis-Dendrochrysanines

Hiroyuki Konno,* Sayako Kusumoto, Sotaro Kanai, Yasuyuki Yamahana, Kazuto Nosaka, and Kenichi Akaji

*Department of Chemistry, Graduate School of Medical Science, Kyoto Prefectural University of Medicine, Kita-ku, Kyoto 603-8334, Japan


Trans- and cis-dendrochrysanines (1 and 2), isolated from the stems of Dendrobium chrysanthum Wall., were first synthesized from L-proline. The absolute configuration of 1 and 2 was established to be S by the syntheses.

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Paper | Regular issue | Vol 68, No. 12, 2006, pp. 2587 - 2594
Published online: 17th October, 2006
DOI: 10.3987/COM-06-10887
Total Synthesis of (±)-2-epi-Validamine

Hiroaki Okamura,* Hiroshi Nagaike, Nsiama Tienabe Kipassa, Tetsuo Iwagawa, and Munehiro Nakatani

*Department of Chemistry and Bioscience, Faculty of Science, Kagoshima University, 1-21-35 Korimoto, Kagoshima 890-0065, Japan


(±)-Validamine and its epimers, (±)-2-epi-validamine (DL-5a-carba-α-mannopyranosylamine) and (±)-2-epi-3-epi-validamine (DL-5a-carba-α-altropyranosylamine) were synthesized from a poly-functionalized bicyclolactam that obtained by a base-catalyzed Diels-Alder reaction of N-tosyl-3-hydroxy-2-pyridone and methyl acrylate. All isomers were prepared via a common key intermediate in six or seven steps.

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Note | Regular issue | Vol 68, No. 12, 2006, pp. 2595 - 2605
Published online: 31st October, 2006
DOI: 10.3987/COM-06-10811
Reduction of Nitroindazoles: Preparation of New Amino and Chloroamino Derivatives

Abdellah Miloudi, Douniazed El Abed, Gerard Boyer,* and Jean-Pierre Galy

*UMR Symbio 6178, case 552, University Paul Cezanne, Avenue Escardrille Normandie-Niemen, 13397 Marseille Cedex 20, France


The synthesis of chloroaminoindazoles by the reduction of the nitro group of indazoles using stannous chloride in alcoholic acid solution is reported. Using catalytic hydrogenation with palladium the expected reduction to amino-indazoles occur.

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Note | Regular issue | Vol 68, No. 12, 2006, pp. 2607 - 2613
Published online: 24th October, 2006
DOI: 10.3987/COM-06-10812
Exclusive Formation of α-Anomers in NbCl5-Promoted Ferrier Rearrangement for the Synthesis of 2,3-Unsaturated Glycosides

Ronaldo N. de Oliveira, Adriana C. N. de Melo, Rajendra M. Srivastava,* and Denis Sinou

*Departamento de Química Fundamental, Universidade Federal de Pernambuco, Cidade Universitária, 50740-540, Recife, PE, Brazil


NbCl5-catalyzed reaction of primary and secondary alcohols with tri-O-acetyl-D-glucal is described. Exclusive formation of α-anomers of eight 2,3-unsaturated glycosides (3a-h) in high yields has been observed. Among eight unsaturated glycosides (3a-h) prepared, two of them (3d,e) are new. A new mechanism of the formation of (3a-h) from tri-O-acetyl-D-glucal and an alcohol assisted by NbCl5 as a catalyst has been suggested.

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Note | Regular issue | Vol 68, No. 12, 2006, pp. 2615 - 2626
Published online: 24th October, 2006
DOI: 10.3987/COM-06-10867
Studies on Pyrazine Derivatives. XLIX. Synthesis and Antibacterial Activity of 6-Methoxypyrazine-2-carboxylic Acid Hydrazide Derivatives

Katarzyna Gobis,* Henryk Foks, Aleksandra Zuralska, and Anna Kedzia

*Department of Organic Chemistry, Medical University of Gdansk, Al. Gen. Hallera 107, 80-416 Gdansk, Poland


The new 6-methoxy-pyrazine derivatives have been synthesized. 6-Methoxy-pyrazine-2-carboxylic acid hydrazide was used as an initial material to obtain mono- and dithioester of hydrazinecarbodithioic acid (2 and 3). Compound (2) in reaction with ethanolamine gave triazole derivative (8) with β-hydoxyethyl substituent in 4-position and hydroxyl group in 6-position of pyrazine ring. Dithioester (3) in a reaction with morpholine cyclized to 1,3,4-oxadiazole (11). The same substrate with alkyldiamines gave the few following derivatives: 1,3-diazacycloalkane derivatives (9 and 10), S-methyl-1,3,4-oxadiazole derivative (12) and 1,2,4-triazoletetrahydropyrimidine (13). The compounds obtained were tested in vitro for their activity towards pathogenic strains of anaerobic and aerobic bacteria. Derivative (9) was the most active against both types of tested strains.

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Note | Regular issue | Vol 68, No. 12, 2006, pp. 2627 - 2633
Published online: 27th October, 2006
DOI: 10.3987/COM-06-10880
Synthesis of 2-Amino-4,5-dihydro-1,3-selenazol-4-ones by Reaction of N,N-Disubstituted Selenoureas with Acetylenedicarboxylate

Mamoru Koketsu,* Koichi Kanoh, and Hideharu Ishihara*

*Division of Instrumental Analysis, Life Science Research Center, Gifu University, 1-1 Yanagito, Gifu, Gifu 501-1193, Japan


Reaction of N,N-disubstituted selenoureas with dimethyl acetylenedicarboxylate afforded 2-amino-5-methoxycarbonylmethylene-4,5-dihydro-1,3-selenazol-4-ones in high yields. The crystal structure of 5-methoxycarbonylmethylene-2-piperidino-4,5-dihydro-1,3-selenazol-4-one was confirmed by X-Ray diffraction. Reaction of the N,N-disubstituted selenoureas with acetylenedicarboxylic acid gave 2-amino-5-carboxymethylene-4,5-dihydro-1,3-selenazol-4-ones in high yields.

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Note | Regular issue | Vol 68, No. 12, 2006, pp. 2635 - 2645
Published online: 2nd November, 2006
DOI: 10.3987/COM-06-10886
Efficient New Approach for the Synthesis of N,N-Dialkylamino-1,2,4-triazoles

Qiang Zhang,* Youyi Peng, and William J. Welsh*

*Department of Pharmacology and the Informartics, University of Medicine and Dentistry of New Jersey, 661 Hoes Lane, Piscataway, New Jersey 00854, U.S.A.


A series of 3-N,N-dialkylamino-4,5-diaryl-1,2,4-triazoles were synthesized in high yield under mild reaction conditions by coupling functionalized arylmagnesiums with isothiocyanates and cyclization with Viehe’s salts. No selective thionation reaction was required for the preparation of carbamoyl derivatives.

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Note | Regular issue | Vol 68, No. 12, 2006, pp. 2647 - 2652
Published online: 27th October, 2006
DOI: 10.3987/COM-06-10893
Synthesis of 2-Amino-1,3-selenazoles by Reaction of N,N-Unsubstituted Selenoureas with α,β-Unsaturated Aldehydes

Mamoru Koketsu,* Koichi Kanoh, and Hideharu Ishihara*

*Division of Instrumental Analysis, Life Science Research Center, Gifu University, 1-1 Yanagito, Gifu, Gifu 501-1193, Japan


2-Dialkylamino-1,3-selenazoles were obtained by the reaction of N,N-unsubstituted selenoureas with α,β-unsaturated aldehydes in alcohol in the presence of ferric chloride at room temperature.

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Note | Regular issue | Vol 68, No. 12, 2006, pp. 2653 - 2661
Published online: 27th October, 2006
DOI: 10.3987/COM-06-10895
Synthesis and Characterization of a Series of Alkyloxadiazolylpyridinium Salts as Perspective Ionic Liquids

Ivana Pibiri, Andrea Pace,* Antonio Palumbo Piccionello, Paola Pierro, and Silvestre Buscemi*

*Dipartimento di Chimica Organica, Università digli Studi di Palermo, Viale delle Scienze, Parco d’Orleans II, 90128 Palermo, Italy


The synthesis of a series of 1,2,4-oxadiazolyl-N-methylpyridinium salts differing in the length and the position of the alkyl chain in the heterocyclic ring and the counter ions is reported. Some features of this new family of salts as perspective ionic liquids are described and the influence of the varying moieties in the modulation of the properties is discussed.

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20 data found. 1 - 20 listed