Regular Issue

Vol. 65, No. 11, 2005

24 data found. 1 - 24 listed
Contents | Regular issue | Vol 65, No. 11, 2005
Published online:
DOI: 10.3987/Contents-05-65-11
Communication | Regular issue | Vol 65, No. 11, 2005, pp. 2583 - 2586
Published online: 13th September, 2005
DOI: 10.3987/COM-05-10520
Photochemical Synthesis of Benzopyrimidosemibullvalenes from Benzopyrimidobarrelenes

Kazue Ohkura,* Mikiko Kudo, Tetsuya Ishihara, Ken-ichi Nishijima, and Koh-ichi Seki

*Faculty of Pharmaceutical Sciences, Health Sciences University of Hokkaido, Ishikari-Tobetsu, Hokkaido 061-0293, Japan


UV irradiation (λ= 254 nm) of 5-fluoro-1,3-dimethyluracil with naphthalene afforded a novel benzopyrimidosemibullvalene derivative with H and F atoms remaining intact on the newly constructed moiety. It was found that the semibullvalene could be derived from the initially produced barrelene derivative during irradiation.

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Communication | Regular issue | Vol 65, No. 11, 2005, pp. 2587 - 2592
Published online: 6th September, 2005
DOI: 10.3987/COM-05-10533
A Ring-opening Cross-metathesis Reaction of N-Trialkylsilyl 2-Azabicyclo[2.2.1]hept-5-en-3-one with Allyltrimethylsilane

Minoru Ishikura,* Miyako Hasunuma, and Kazuo Yanada

*Faculty of Pharmaceutical Sciences, Health Sciences University of Hokkaido, Ishikari-Tobetsu, Hokkaido 061-0293, Japan


Subjection of N-trialkylsilyl-2-azabicyclo[2.2.1]hept-5-en-3-one (1) to a ring-opening cross-metathesis reaction with allyltrimethylsilane in the presence of Grubbs’ catalyst was found to allow the predominate formation of pyrrolidine (3) over pyrrolidine (4).

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Paper | Regular issue | Vol 65, No. 11, 2005, pp. 2593 - 2603
Published online: 19th August, 2005
DOI: 10.3987/COM-05-10469
Palladium-catalysed Synthesis of Pyrimidines

Truls Ingebrigtsen, Irene Helland, and Tore Lejon*

*Faculty of Science, Departmentof Chemistry, University of Tromsø, N-9037 Tromsø, Norway


Satisfactory yields of 4-substituted pyrimidines and bicyclic pyrimidines are produced from α-methyl or α-methylene ketones when reacted with formamide and tetrakis(triphenylphosphine)palladium(0) or a 1:2 mixture of palladium(II) acetate and triphenylphosphine as catalysts. Under the same reaction conditions pyridines or imidazole are formed from 1,3- or 1,2-diketones.

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Paper | Regular issue | Vol 65, No. 11, 2005, pp. 2605 - 2618
Published online: 26th August, 2005
DOI: 10.3987/COM-05-10477
Natural Bond Orbital Analysis of Pericyclic and Pseudopericyclic 1,5-Electrocyclizations of Conjugated Azides

Kazuaki Fukushima* and Hideo Iwahashi

*Wakayama Medical University, Wakayama Medical University


We have carried out calculations of energetic, structural and electronic properties for 1,5-electrocyclizations of conjugated azides at the B3LYP/6-31+G(d) level of theory. Analyses of the second-order perturbative energy lowering for interaction between donor and acceptor natural bond orbitals at the RHF/6-31+G(d) level of theory have revealed conjugated group dependent pericyclic and pseudopericyclic nature of the reactions.

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Paper | Regular issue | Vol 65, No. 11, 2005, pp. 2619 - 2634
Published online: 13th September, 2005
DOI: 10.3987/COM-05-10491
Synthesis and Structure of Dipyrido-1,4-dithiins

Beata Morak, Krystian Pluta,* Kinga Suwinska, Miroslawa Grymel, Céline Besnard, Marc Schiltz, Christian Kloc, and Theo Siegrist

*Department of Organic Chemistry, The Medical University of Silesia, Jagielloñska 4, 41-200 Sosnowiec, Poland


Synthesis, properties and reactions of two isomeric dipyrido-1,4-dithiins of the C2h and C2v symmetry are described. Their structure determination and identification are based on spectroscopic methods (1H and 13C NMR, HETCOR, gHMBC and MS), physical properties (mp and Rf), the 1,4-dithiin ring opening reactions and finally X-Ray analysis. A very unusual type of the Smiles rearrangement (S→S, the pyridyl group migrates from one sulfur atom to another) during the 1,4-dithiin ring opening with sodium methanethiolate enabling isomerization of dithiin with the C2h symmetry to dithiin with the C2v symmetry is found.

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Paper | Regular issue | Vol 65, No. 11, 2005, pp. 2635 - 2647
Published online: 19th August, 2005
DOI: 10.3987/COM-05-10494
Stereocontrolled Synthesis of New Tetrahydrofuro[2,3-d]thiazole Derivatives via Activated Vinylogous Iminium Ions

Rade Markovic,* Marija Baranac, Peter Steel, Erich Kleinpeter, and Milovan Stojanovic

*Faculty of Chemistry, University of Belgrade, Studentski trg 16, P.O.Box 158, 11001 Belgrade, Serbia and Montenegro


Heterocyclization of (Z)-5-(2-hydroxyethyl)-3-methyl-4-oxothiazo-lidines, bearing electron-withdrawing groups conjugated to an exocyclic double bond at C(2)-position, afforded under reductive conditions, cis-tetrahydro-furo[2,3-d]thiazole derivatives. The reactions of these functionalized push-pull β-enamines occur in a stereocontrolled fashion via activated vinylogous N-methyliminium ions, which are trapped by an internal hydroxyethyl group.

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Paper | Regular issue | Vol 65, No. 11, 2005, pp. 2649 - 2655
Published online: 6th September, 2005
DOI: 10.3987/COM-05-10497
Synthesis of 4,6-Diaryl-4,6,7,8-tetrahydro[1,4]oxazepino[4,3-c]sydnone

Zhanbin Zhang* and Xinfang Duan

*Department of Chemistry, Beijing Normal University, Beijing, 100875, China


Seven-membered ring fused sydnones, 4,6-diaryl-4,6,7,8-tetrahydro[1,4]oxazepino[4,3-c]sydnones (2) were prepared via oxa-Pictet-Spengler reaction of 3-(3-phenyl-3-hydroxypropyl)sydnone (1) with aromatic aldehydes in the presence of Lewis acid. The reactions gave two stereoisomers ( cis- and trans-), and the cis- isomers were the major products.

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Paper | Regular issue | Vol 65, No. 11, 2005, pp. 2657 - 2665
Published online: 2nd September, 2005
DOI: 10.3987/COM-05-10500
Asymmetric Synthesis of (2R,3R,4R)-3-Hydroxy-4-methylproline via Chromium(II) Chloride-mediated Coupling Reactions of (S)-Garner Aldehyde with Crotyl Bromide

Haruko Inaba, Yukiko Hiraiwa, Satoshi Yoshida, Mina Tamura, Asako Kuroda, Aki Ogawa, Yutaka Aoyagi, Akihiro Ohta, and Koichi Takeya*

*School of Pharmacy, Tokyo University of Pharmacy and Life Science, 1432-1 Horinouchi, Hachioji, Tokyo 192-0392, Japan


Efficient synthesis of (2R,4R,4R)-3-hydroxy-4-methylproline (1a), which is an antipode of the component of potent antifungal echinocandins, from (S)-Garner aldehyde (2a) has been established. The key step is chromium(II) chloride-mediated coupling reactions with crotyl bromide giving homoallyl alcohols (4a) and (4a’) in a ratio of 83:17.

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Paper | Regular issue | Vol 65, No. 11, 2005, pp. 2667 - 2674
Published online: 19th August, 2005
DOI: 10.3987/COM-05-10504
New Synthesis of t-Butyl 1,2-Dihydro-1-oxaazulene-3-carboxylates Using Lithium Trimethylsilyldiazomethane

Susumu Tsuchida, Yoshiyuki Hari, and Toyohiko Aoyama*

*Graduate School of Pharmaceutical Sciences, Nagoya City University, 3-1 Tanabe-dori, Mizuho-ku, Nagoya 467-8603, Japan


Lithium trimethylsilyldiazomethane reacts with t-butyl aryloxypyruvates to give t-butyl 1,2-dihydro-1-oxaazulene-3-carboxylates via alkylidenecarbene intermediates.

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Paper | Regular issue | Vol 65, No. 11, 2005, pp. 2675 - 2682
Published online: 26th August, 2005
DOI: 10.3987/COM-05-10505
Five New Sulfur-containing Polybrominated Bisindoles from the Red Alga Laurencia brongniartii

Natsuki K. Kubota, Hajime Iwamoto, Yoshimasa Fukazawa, and Yasuto Uchio*

*School of Allied Medical Sciences, Faculty of Medicine, Kagoshima University, Kagoshima 890-8544, Japan


Five new sulfur-containing polybrominated bisindole (1˜5) were isolated from the red alga, Laurencia brongniartii, in addition to six related compounds (6˜11), which have been previously found in the Okinawan alga. The structures of these new bisindole metabolites were elucidated on the basis of spectroscopic studies, as well as X-Ray crystallographic analysis of 1.

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Paper | Regular issue | Vol 65, No. 11, 2005, pp. 2683 - 2692
Published online: 16th August, 2005
DOI: 10.3987/COM-05-10518
The First and Reliable Synthesis of Thieno[2,3-e][1,2,4]triazolo[1,5-c]pyrimidin-5(6H)-ones via Their [4,3-c] Compounds by Dimroth Rearrangement

Tomohisa Nagamatsu* and Shoeb Ahmed

*Faculty of Pharmaceutical Sciences, Okayama University, Tsushima-naka 1-1-1, Okayama 700-8530, Japan


This paper describes a reliable and general synthesis of thieno[2,3-e][1,2,4]triazolo[1,5-c]pyrimidin-5(6H)-one (5a) and its 2-substituted derivatives (5b-i) as a novel ring system prepared by nimble isomerization of their [4,3-c] compounds (4a-i), which were produced by condensation of 4-hydrazinothieno[3,2-d]pyrimidin-2(1H)-one (12) with appropriate triethyl orthoesters or by oxidative cyclization of 4-(benzylidenehydrazino)thieno[3,2-d]pyrimidin-2(1H)- ones (13c-i). The [1,5-c] isomers (5a-c) were further prepared by condensation of 3-amino-4-imino-2-oxo-1,2,3,4-tetrahydrothieno[3,2-d]pyrimidine (16) with appropriate triethyl orthoesters as a synthetic method for a reliable structure of the tricyclic ring systems.

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Paper | Regular issue | Vol 65, No. 11, 2005, pp. 2693 - 2703
Published online: 26th August, 2005
DOI: 10.3987/COM-05-10522
Synthesis of 3-Methoxyellipticine and Ellipticine by Friedel-Crafts Reaction of Indole-2,3-dicarboxylic Anhydride and Selective Demethylation

Yasuyoshi Miki,* Yoshiyuki Aoki, Yasuhiko Tsuzaki, Misako Umemoto, and Hajime Hibino

*Faculty of Pharmaceutical Sciences, Kinki University, 3-4-1, Kowakae, Higashi-Osaka 577-8502, Japan


Reaction of 1-benzylindole-2,3-dicarboxylic anhydride with 2,4,6-trimethoxypyridine in the presence of a Lewis acid gave 1-benzyl-3-(2,4,6-trimethoxynicotinoyl)indole-2-carboxylic acid as the sole product in high yield, which could be changed to 1-benzyl-3-(2,4,6-trimethoxynicotinoyl)indole. 1 Benzyl-3 (2,4,6-trimethoxynicotinoyl)indole was converted to 3 methoxy¬ellipticine and ellipticine by selective demethylation and triflation of the methoxy group.

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Paper | Regular issue | Vol 65, No. 11, 2005, pp. 2705 - 2720
Published online: 13th September, 2005
DOI: 10.3987/COM-05-10530
Isothiazolo[3,2-b]-1,3,4-oxadiazole-5,5-dioxide: Synthesis of a New Heteropentalene System

Stephan Schmidt, Arne Kolberg, Lothar Hennig, Jens Hunger, and Bärbel Schulze*

*Department of Organic Chemistry, Leipzig University, Johannisallee 29, Leipzig 04103, Germany


Monocyclic, acceptor-substituted N-aroylisothiazolium-2-imines (5a-d), easily available by cyclocondensation of 2-methyl-3-thiocyanato-2-butenal with aryl hydrazides, are described and the structure of new five-membered azomethine imines (5) is determined by X-Ray structure of 5a. The oxidation of 2-imines (5) with hydrogen peroxide in acetic acid gives 3-hydroperoxysultims (rac-cis 6) , -sultams (7), and 3-oxosultams (10). The 3-hydroxysultams (8a-d) are obtained by reduction of hydroperoxides (7). Surprisingly, after the dehydration of 8a-h and its 1,5-electrocyclization, a new type of heteropentalenes, the isothiazolo[3,2-b]-1,3,4-oxadiazole-5,5-dioxides (11) is formed.

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Paper | Regular issue | Vol 65, No. 11, 2005, pp. 2721 - 2728
Published online: 16th September, 2005
DOI: 10.3987/COM-05-10531
Synthesis of 1,2-Disubstituted Imidazoles via Cross-Coupling and Substitution Reactions

Ingo Langhammer and Thomas Erker*

*Department of Medicinal/Pharmaceutical Chemistry, University of Vienna, Althanstrasse 14, A-1090 Wien, Austria


Lithiation of imidazole compound (1) in position 2 and subsequent quenching with electrophiles provided a route to 1,2-diaryl-, 1-aryl-2-cycloalkyl- and 1-aryl-2-heterocyclyl-substituted imidazoles.

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Note | Regular issue | Vol 65, No. 11, 2005, pp. 2729 - 2740
Published online: 2nd September, 2005
DOI: 10.3987/COM-05-10440
A Facile Synthesis of 2-Aminothiazolo[5,4-b]pyridines and 2-Aminobenzoxazoles via Cyclization of Thioureas

Ju Hee Yoon, Hyunmin Song, Sang Wong Kim, Gyoonhee Han, and Hea-Young Park Choo*

*Ewha Womans University, School of Pharmacy, Seoul 120-750, Korea


2-Aminothiazolo[5,4-b]pyridines and 2-aminobenzoxazoles have been synthesized from 2-hydroxy-3-thioureidopyridine and 2-hydroxy-3- thioureidobenzene respectively via acid catalyzed cyclization, which were prepared by the reaction of isothiocyanates with 2-hydroxy-3-aminopyridine or 2-aminophenol. The hydroxyl group of N-(2-hydroxy-5-phenyl)- N’-phenyl thiourea reacted as nucleophile to thioureido carbon to give 2-aminobenzoxazoles, whereas that of N-(2-hydroxypyridino)-N’-phenylthiourea was reacted as leaving group upon nuclephillic sulfur of thiourea group in the presence of trifluoroacetic acid or phosphoric acid.

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Note | Regular issue | Vol 65, No. 11, 2005, pp. 2741 - 2751
Published online: 19th August, 2005
DOI: 10.3987/COM-05-10461
Synthesis of Substituted 1,3-Dimethyl-1H-quinoxalin-2-ones from Aniline Derivatives

Xun Li, Donghua Wang, Jifeng Wu, and Wenfang Xu*

*College of Pharmacy, Shangdong University, Jinan 250012, China


Substituted 1,3-dimethyl-1H-quinoxalin-2-ones (7) have been synthesized through the procedures of acylation, nitration, reduction, intramolecular alkylation, oxidation, and N-methylation starting from 3,4-disubstituted aniline.

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Note | Regular issue | Vol 65, No. 11, 2005, pp. 2753 - 2761
Published online: 16th September, 2005
DOI: 10.3987/COM-05-10499
Comparative Structural Studies of 4-Diazopyrazole Derivatives by X-Ray Diffraction and Theoretical Investigation

Giuseppe Daidone,* Benedetta Maggio, Maria Valeria Raimondi, Gabriella Bombieri, Nicoletta Marchini, and Roberto Artali

*Department of Pharmaceutical Chemistry and Technology, University of Palermo, Via Archirafi 32, 90123 Palermo,


The X-Ray crystal and molecular structures of the 4-pyrazol derivatives 3-methyl-4-diazo-5-benzamido-1H-pyrazole (4) and 3-benzamido-5-methyl-1H-pyrazole (3) have been determined. A dimeric structure has been found for the first and polymeric for the second. A comparison of 4 with 1,3-dimethyl-4-diazo-5-benzamido-1H-pyrazole (2) shows differences in the geometrical parameters of the pyrazole ring due to electron delocalization in 2 consequent to the nitrogen negative charge in the latter. Theoretical investigation at the density functional theory (DFT) level shows difference in the molecular electronic distribution of 2 and 4, in agreement with the structural parameters and the IR stretching frequencies of the respective carbonyl moieties.

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Note | Regular issue | Vol 65, No. 11, 2005, pp. 2763 - 2770
Published online: 19th August, 2005
DOI: 10.3987/COM-05-10511
A Practical Synthesis of 1-Alkyl-3-amino-4-aryl-1,8-naphthyridin-2-(1H)-one, a Partial Structure of ACAT Inhibitor SMP-797

Hitoshi Ban,* Masami Muraoka, Kouji Morisita, and Naohito Ohashi

*Research Division, Sumitomo Pharmaceuticals Co., Ltd., 1-98, Kasugadenaka 3-chome, Konohana-ku, Osaka 554-0022, Japan


3-Amino-4-[3-(3-benzyloxypropoxy)phenyl]-1-butyl-1,8- naphthyridin-2(1H)-one, which is a naphthyridine part of a potent ACAT (acyl-CoA: cholesterol acyltransferase) inhibitor SMP-797, was effectively synthesized from m-bromophenol in 5 steps without isolating intermediates. The synthesis involved the intramolecular aldol reaction as a key step.

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Note | Regular issue | Vol 65, No. 11, 2005, pp. 2771 - 2776
Published online: 26th August, 2005
DOI: 10.3987/COM-05-10523
New Vermistatin Derivatives Isolated from Penicillium simplicissimum

Shin-ichirou Komai, Tomoo Hosoe, Takeshi Itabashi, Koohei Nozawa, Takashi Yaguchi, Kazutaka Fukushima, and Ken-ichi Kawai*

*Faculty of Pharmaceutical Sciences, Hoshi University, 2-4-41 Ebara, Shinagawa-ku, Tokyo 142-8501, Japan


Four new vermistatin derivatives, dihydrovermistatin (1), acetoxy- dihydrovermistatin (2), hydroxydihydrovermistatin (3), and penisimplicissin (4) were isolated along with vermistatin (5), penicillide, and funicone from the extract of Penicillium simplicissimum IFM 53375. The structures of 1 - 4 were determined by spectroscopic and chemical methods.

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Note | Regular issue | Vol 65, No. 11, 2005, pp. 2777 - 2782
Published online: 16th September, 2005
DOI: 10.3987/COM-05-10534
Friedländer Reactions of Triacetylmethane - Unusual Distribution of Products -

A. F. M. Motiur Rahman, Youngjoo Kwon, and Yurngdong Jahng*

*College of Pharmacy, Yeungnam University, Kyongsan 712-749, Korea


Friedländer reactions of triacetylmethane with selected β-amino-α,β- unsaturated aldehydes afforded pyridoheterocycles and their 2-methyl derivatives instead of triheteroarylmethane.

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Note | Regular issue | Vol 65, No. 11, 2005, pp. 2783 - 2790
Published online: 6th September, 2005
DOI: 10.3987/COM-05-10535
Synthesis of Benzobicyclo[2.2.1]heptylimidazoles as Conformationally Constrained Adrenergic Receptor Antagonists

Jari Yli-Kauhaluoma,* Aki Laine, Jari Ratilainen, and Arto Karjalainen

*Technical Research Centre of Finland, VTT Processes, P.O. Box 1602, FI-02044 VTT, Finland


A facile method for the preparation of conformationally rigid analogues of the adrenergic α-2 receptor antagonist atipamezole and the adrenergic α-2 receptor agonist medetomidine has been developed. The efficient benzyne [4+2] cycloaddition reaction was used to give the core 7-acetylbenzonorbornadiene structure, which was subsequently elaborated to the corresponding imidazole-based syn and anti isomers by means of the classical Bredereck’s method.

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Note | Regular issue | Vol 65, No. 11, 2005, pp. 2791 - 2798
Published online: 13th September, 2005
DOI: 10.3987/COM-05-10536
Synthesis of Novel Triphenylene-Type Cations Containing Both Thiophene Rings and a Tropylium Ion Ring. Cyclohepta[e]thieno[2,3-g]benzodithiophenylium Ion and Cyclohepta[e]thieno[3,2-g]benzodithiophenylium Ion

Teppei Oyanagi, Yasuhiro Sakurai, and Kimiaki Yamamura*

*Department of Chemistry, Faculty of Science, Kobe University, Nada, Kobe 657-8501, Japan


An isomeric pair of cyclohepta[e]thieno[g]benzodithiophenylium ions has been synthesized by an intramolecular Friedel-Crafts type reaction of 2(3)-thienyl-3(2)-cycloheptatrienylthiophenes in a one-pot reaction. These are the isoelectronic cations of triphenylene having both electron-rich and electron-deficient aromatic rings, thiophene and tropylium ion, respectively, in place of phenyl rings.

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Note | Regular issue | Vol 65, No. 11, 2005, pp. 2799 - 2807
Published online: 13th September, 2005
DOI: 10.3987/COM-05-10537
New Approach to the Synthesis of Non-benzenoid Aromatic Compounds, Functionalized 1-Azaazulene Derivatives: Cyclization Reactions of 2-Substituted Tropones with N-Silylenamine and Enamine

Norio Sakai, Naoto Hattori, Nanako Tomizawa, Noritaka Abe, and Takeo Konakahara*

*Department of Pure and Applied Chemistry, Faculty of Science and Technology, Tokyo University of Science, Noda, Chiba 278-8510, Japan


The reaction of enamines with 2-subsituted tropones produced functionalized 1-azaazulene derivatives. When the reaction is conducted in an aprotic solvent, such as DMSO, the desired 1-azaazulene was obtained in 51% yield. The introduction of an electron-donating group on the enamine increased its nucleophilicity and improved the product yield. On the other hand, the reaction of enamines with 4-isopropyltropone-2-tosylate afforded a different 1-azaazulene derivative.

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24 data found. 1 - 24 listed