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. 41, No. 12, 1995
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■ Synthesis, Property, and X-Ray Crystal Structure of New Dibenzophosphaselenocines
Hisashi Fujihara,* Tohru Nishioka, Hisatomo Mima, and Naomichi Furukawa*
*Department of Chemistry, University of Tsukuba, Tsukuba, Ibaraki 305, Japan
Abstract
New phosphorus-selenium heterocycles, dibenzophosphaselenocines (1 and 2), have been prepared. The structure of the dibenzophosphaselenocines was determined by multinuclear nmr spectroscopy and X-ray diffraction analysis.
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■ 4',1'a-Methanocarbocyclic Adenosine Analogues as Potential Inhibitors of S-Adenosylhomocysteine Hydrolase
Lak S. Jeong, Victor E. Marquez,* Chong-Shen Yuan, and Ronald T. Borchardt
*Laboratory of Medicinal Chemistry, Developmental Therapeutics Program, Division of Cancer Treatment, National Cancer Institute, NIH, Bethesda, Maryland 20892, U.S.A.
Abstract
Cyclopropane-fused carbocyclic adenosine (4) and its 5’-carboxaldehyde analogue (5) were synthesized as potential inhibitors of S-adenosylhomocysteine hydrolase. The key bicyclo[3.1.0]hexane alcohol (8) was obtained from the optically pure cyclopentenone synthon (6), and attachment of the purine base was performed in a single step from the methylsulfonate ester of 8 (compound (9)). Both target compounds behaved as weak inhibitors of the hydrolase.
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■ Reaction of 1-Pyridiniothiobenzoylaminides with Dimethyl Acetylenedicarboxylate
Akikazu Kakehi, * Suketaka Ito, Fumihito Ishida, and Yoshinori Tominaga
*Department of Chemistry and Material Engineering, Faculty of Engineering, Shinshu University, Wakasato, Nagano 380, Japan
Abstract
The reactions of 1-pyridiniothiobenzoylaminides with dimethyl acetylenedicarboxylate in chloroform at 50-60 °C provided dimethyl 5-thia-2,3-diazatricyclo[4.3.2.02,7]undeca-3,8,10-triene-6,11-dicarboxylate derivatives in moderate yields. The structures of these products were assumed by their spectral and analytical data and determined finally by the X-ray analysis of one compound.
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■ Acetylations of (±)-Agelasimine-A and (±)-Agelasimine-B: A Racemic Synthesis of Purino-Diterpene Derived from Antimicrobial Metabolites of Agelas mauritiana
Masashi Ohba*, Nobuo Kawase, and Tozo Fujii
*Faculty of Pharmaceutical Sciences, Kanazawa University, Takara-machi, Kanazawa 920, Japan
Abstract
The reaction of (±)-agelasimine-A [(±)-3a] with acetic anhydride in pyridine yielded the imidazole derivative [(±)-5a], which was found to correspond to "diacetylagelasimine-A". A similar acetylation of (±)-agelasimine-B [(±)-4a] provided (±)-7a and (±)-2a. On treatment with boiling 50% aqueous EtOH, (±)-7a gave (±)-2a and the dihydrohypoxanthine derivative [(±)-8a]. It is suggested that purino-diterpene (2a), isolated from the acetylated mixture of the crude extract of the sponge Agelas mauritiana, might have originated from agelasimine-B (4a) through N6-acetylagelasimine-B (7a).
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■ Efficient and Regioselective Photocyclization Reactions of N-[(ω-Trimethylsilylmethoxy)polyoxalkyl]phthalimides to Azacrown Ethers
Ung Chan Yoon*, Sun Wha Oh, and Chan Woo Lee
*Department of Chemistry, College of Natural Sciences, Pusan National University, Pusan 609-735, Korea
Abstract
Single electron transfer induced photocyclization reactions of N-[(ω-trimethylsilylmethoxy)polyoxalkyl]phthalimides have been explored. Photocyclizations occur in methanol in modest to high yield to produce cyclized products in which phthalimide carbonyl carbon is bonded to the ω-carbon of side chain in place of the trimethylsilyl group. The efficient, chemoselective, and regioselective cyclization reactions represent synthetically useful processes for construction of azacrown ethers of various sizes.
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■ Substrate Specificity of Vinorine Hydroxylase, a Novel Membrane-bound Key Enzyme of Rauwolfia Indole Alkaloid Biosynthesis
Heike Falkenhagen, Leo Polz, Hiromitsu Takayama, Mariko Kitajima, Shin-ichiro Sakai, Norio Aimi, and Joachim Stöckigt*
*Institute of Pharmacy, Johannes Gutenberg-Universität Mainz, Staudinger Weg 5, 55099 Mainz, Germany
Abstract
The novel membrane bound enzyme vinorine hydroxylase exhibits an extraordinary high substrate specificity which points to its key function in the biosynthesis of monoterpenoid indole alkaloids of the ajmaline type in cell suspension cultures of the Indian medicinal plant Rauwolfia serpentina.
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■ Photosynthesis of Heteropolycyclic Diquinolones Twofold Photodehydrohalogenation Reaction of Benzo[1,2-b:4,5-b']dithiophene- and Dithieno[3,2-b:2',3'-d]thiophenedicarboxanilides
Miro Malesevic, Grace Karminski-Zamola*, Miroslav Bajic, and David W. Boykin
*Department of Organic Chemistry, Faculty of Chemical Engineering and Technology, University of Zagreb, 41000 Zagreb, Croatia
Abstract
Heteropolycyclic diquinolones; benzo[1,2-b:4,5-b']dithieno[2',3'-c':2",3"-c"]-5,13-N,N'-dimethyldiquinoline-6,14-dione (9) and dithieno[3,2-b:2',3'-d]thienyl[2",3"-c:2",3"-c']-5,10-N,N-dimethyldiquinoline-6,9-dione (17) are prepared by twofold photochemical dehydrohalogenation reaction of corresponding benzodithiophene- and dithienothiophenedicarboxanilides; 3,7-dichloro-N,N'-dimethylbenzo[1,2-b:4,5-b']dithiophene-2,6-dicarboxanilide (8) and 3,5-dichloro-N,N'-dimethyldithieno[3,2-b:2',3'-d]thiophene-2,6-dicarboxanilde (16). The products of onefold photochemical dehydrohalogenation reaction, anilidoquinolones; 9-chloro-10-N'-methylanilidobenzo[1,2-b:4,5-b']dithieno[2,3-c']-5-N-methylquinolin-6-one (10) and 10-chloro-9-N'-methylanilidodithieno[3,2-b:2',3'-d]thienyl[2",3"-c']-5-N-methylquinolin-6-one (18) were also isolated to prove the mechanism of the reaction.
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■ A Controlled Stepwise Oxidation of Ethyl 2-Oxothiazolidine-4-carboxylate to the Corresponding 2-Hydroxythiazole
Gloria Serra, David González, and Eduardo Manta*
*Cátedra de Química Farmacéutica, Facultad de Química, Universidad de la República, Av. General Flores 2124. C. C. 1157, 11800 Montevideo, Uruguay
Abstract
Methyl 2-hydroxythiazole-4-carboxylate was obtained via a controlled stepwise oxidative procedure from the corresponding 2-oxothiazolidine. A series of intermediates have been isolated and characterized, supporting the ionic and radical mechanisms already proposed in the literature.
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■ Substituted Benzimidazoles. Part 1. Synthesis and Properties of Some 2-Aryl-5-fluoro-6-(4-methyl-1-piperazinyl)-1H-benzimidazoles
Mustafa M. El-Abadelah*, Salim S. Sabri, Musa H. Abu Zarga, and Raid J. Abdel-Jalil
*Chemistry Department , University of Jordan, Amman, Jordan
Abstract
2-Aryl-5-fluoro-6-(4-methyl-1-piperazinyl)benzimidazoles (8a-k) were synthesized for bioassay via interaction of 4-fluoro-5-(4-methyl-1-piperazinyl)-1,2-diaminobenzene (6) with the appropriate aldehyde. The intermediate Schiff bases (7a-k) were isolated and converted, thermally in nitrobenzene, to the respective heterocycles (8a-k). However, none of the tested model compounds (8c-e) showed any significant in vitro activity against Pseudomonas aeruginosa, Staphylococcus aureus, Aspergillus parasiticus and Candida albicans at concentration < 100 μg/ml.
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■ Stereoselective Reduction of the Double Bond in Δ5-3-Oxo-4-azasteroids
Jacek W. Morzycki,* Agnieszka Z. Wilczewska, Ewa Zochowska, and Zenon Lotowski
*Institute of Chemistry, University of Warsaw, Bialystok Branch, Pilsudskiego 11/4, 15-443 Bialystok, Poland
Abstract
The stereoselective borohydride/H+ reduction of the C(5)-C(6) double bond in Δ5-3-oxo-4-azasteroids has been studied. The intermediate acylimine is preferentially attacked by borohydride from the α side. The optimization with respect to the type of borohydride, solvent, catalyst and temperature has been carried out.
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■ Synthesis of 2-Substituted Isothiazolo[5,4-b]pyridin-3(2H)-one 1,1-Dioxides
Victor Martinez-Merino,* Maria J. Gil, Jose M. Zabalza, and Alberto Gonzalez
*Departamento de Química, Universidad Pública de Navarra, 31006 Pamplona, Spain
Abstract
The isothiazole[5,4-b]pyridin-3(2H)-one 1,1-dioxides (3a-g) were prepared from the corresponding isothiazolo[5,4-b]pyridin-3(2H)-ones (1a-g) by means of an oxidation with oxone® (KHSO5) and sodium hypochlorite (NaOCl) in two steps. The influence of the substituents (R), in position 2 of this system, on the oxidation process was studied. While the oxidation of 1a-g with 3-chloroperoxybenzoic acid gave yields of 3a-g depending greatly on the nature of R, the combined KHSO5/NaOCl method gave good yields of 3a-g in all of the cases studied.
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■ Synthesis of 17- and 21-Membered Macrocycles Incorporating the Chiral 1,1'-Binaphthyl Backbone and Nitrogen, Oxygen, and Phosphorus Donor Atoms
Petra Wimmer, Gerd Klintschar, and Michael Widhalm*
*Institut für Organische Chemie, Universität Wien, 1090 Wien, Austria
Abstract
A 17-membered diaza-diphospha- and a 21-membered diaza-dioxadiphospha-macrocycle (6) and (12), respectively, including the inherent chiral binaphthyl moiety were synthesized. Titanium(IV) mediated cyclization of 1,1’-binaphthyl-2,2’-dicarbaldehyde (4) with 1,3-bis[(2-aminophenyl)phenylphosphino]propane (8) and subsequent reduction afforded 6a-c as a mixture of three diastereomers in 14% overall yield. Ligand (12) was obtained from the nickel amido complex of 8 and 2,2’-bis[2-(4-toluene)sulfonyloxyethoxy]-1,1’-binaphthyl (10a) by a template synthesis in the presence of Cs2CO3 in 63% yield. X-Ray structure determinations of cationic Ni(II) complexes of 6a and 12 were performed.
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■ Ficusins A and B, Two New Cyclic-Monoterpene-substituted Isoflavones from Ficus septica Barm. F.
Miwa Aida, Yoshio Hano, and Taro Nomura*
*Faculty of Pharmaceutical Sciences, Toho University, 2-2-1, Miyama, Funabashi, Chiba 274, Japan
Abstract
Two new cyclic-monoterpene-substituted isoflavones, ficusins A (1) and B (2) were isolated from the Indonesian moraceous plant, Ficus septica Barm. F. The structures of ficusins A and B were shown to be 1 and 2, respectively, on the basis of spectroscopic data.
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■ Synthesis of N-Substituted 3-Aminomethyl-2,3-dihydrofuro[2,3-c]pyridines, Potent Serotoninergic Ligands
Benoît Joseph, Abdelhakim Benarab, and Gérald Guillaumet*
*Laboratoire de Chimie Bioorganique et Analytique associé au CNRS, Université d'Orléans, BP 6759, 45067 Orléans Cedex 2, France
Abstract
Regioselective lithiation of 2-chloro-3-oxiranylmethoxypyridine, followed by intramolecular epoxide ring-opening reaction provided (7-chloro-2,3-dihydrofuro[2,3-c]pyridin-3-yl)methanol (1). Multistep synthesis from 1 gave a variety of N-substituted 3-aminomethyl-2,3-dihydrofuro[2,3-c]pyridines as potent serotoninergic ligands.
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■ Reaction of 4-Amino-1,2,4-triazolium Salts with Polarized Olefins
Yoshiro Matsuda*, Yasusige Chiyomaru, Kazuki Furuno, and Takanobu Nishiyori
*School of Pharmaceutical Sciences, Nagasaki University, 1-14 Bunkyo-machi, Nagasaki 852, Japan
Abstract
The reaction of 4-amino-1,2,4-triazolium salts (5a,b) with polarized olefins (3a,b, 4a) in the presence of K2CO3 in EtOH or DMSO directly yielded the back-donated 1,6-cyclization products, mesomeric betaines (6a-c, 7a,b) via N-vinylimino ylides, while the reaction of the salts (5a,b) with polarized olefins (4b,c) gave the 1,5-dipolar cyclization products, pyrazoles (10a, b) and [1,2,4]triazolo[4,3-b]pyrazole (11).
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■ New Diels-Alder Reactions of Oxy-functionalized 3-Vinylindoles with Carbodienophiles
Ulf Pindur* and Martina Rogge
*Department of Chemistry and Pharmacy, Institute of Pharmacy, University of Mainz, Saarstrasse 21, D-55122 Mainz, Germany
Abstract
Some new Diels-Alder reactions of oxy-functionalized 3-vinylindoles (1, 2) with carbodienophiles are described. In most cases, functionalized carbazoles (4 - 6, 10 and 11) were formed regio- and/or endo-selectively. The product spectrum is characterized by [4+2] cycloadditions, elimination and ene reaction.
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■ Trichilinins B and C, Two New Limonoids from Melia toosendan
Jian-Bo Zhou, Hiroaki Okamura, Tetsuo Iwagawa, Yumiko Nakamura, Noboru Nakayama, Kenjiro Tadera, and Munehiro Nakatani*
*Department of Chemistry, Faculty of Science, Kagoshima University, Korimoto, Kagoshima 890, Japan
Abstract
Two new limonoids, trichilinins B and C, were isolated along with four nimbolidins and salannin from the root bark of Melia toosendan.
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■ Synthesis of 6-Substituted 2-Phenyloxazolo[4,5-b]pyridines
Marie-Claude Viaud, Patricia Jamoneau, Laurence Savelon, and Gérald Guillaumet*
*Laboratoire de Chimie Bioorganique et Analytique associé au CNRS, Université d'Orléans, BP 6759, 45067 ORLEANS Cedex 2, France
Abstract
The synthesis of 2-phenyloxazolo[4,5-b]pyridines substituted in position 6 by alkyl, aryl, benzyl, formyl, acetyl, benzoyl and nitrile group is described.
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■ Sorocenols C-F, Four New Isoprenylated Phenols from the Root Bark of Sorocea bonplandii Baillon
Yoshio Hano, Juntaro Yamanaka, Yasunori Momose, and Taro Nomura*
*Faculty of Pharmaceutical Sciences, Toho University, 2-2-1, Miyama, Funabashi, Chiba 274, Japan
Abstract
From the root bark of Sorocea bonplandii Baillon (Moraceae), collected in Paraguay, four new isoprenylated phenols, sorocenols C (1), D (2), E (3), and E (4) were isolated along with four known isoprenylated phenols, mulberrofuran K (5), kuwanon J (6), chalcomoracin (7), and kuwanol E (8). The structures of sorocenols C -F were shown to be 1 - 4, respectively. These compounds are regarded as variations of Diels-Alder type adducts between chalcone derivatives and dehydroisoprenylated phenols.
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■ Facile Preparation of (3S)-1,3-Dimethyl-3-cyanomethyl-5-ethoxyoxindole from Julian's Nitrile Enriched in the (3S)-Enantiomer
Xue-Feng Pei* and Arnold Brossi
*Laboratory of Bioorganic Chemistry, NIDDK, NIH, Bldg. 8, Rm. 1A-20, Bethesda, MD 20892, U.S.A.
Abstract
(3S)-1,3-Dimethyl-3-cyanomethyl-5-ethoxyoxindole (4a) was prepared in high optical purity from a 4a enriched enantiomeric mixture obtained by asymmetric 3-cyanomethylation of oxindole (11) by removal of the racemate a single recrystallization.
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■ Chemistry of Persistent Free Bi- and Polyradicals
Mohab-Eddine Brik
*Laboratoire de Chimie Structurale Organique, ICMO URA CNRS 1384, Bat 410, Université de Paris-Sud, 91405 Orsay Cedex, France
Abstract
The aim of this paper is to provide an overview of important developments in the chemistry and the use of persistent free bi- and polyradicals to study chemical and biological model systems by electron paramagnetic resonance (epr) or as materials for physical purposes. The paper also discusses the different ways used to synthesize these molecules by structure modifications of carboxylic and heterocyclic nitroxides as well as their diamagnetic precursors. The review tries to sum up our knowledge of these strong paramagnetic species with the aim of drawing the reader’s attention to their application in recent fields of physics, chemistry, biochemistry, biology and and medical radiology including magnetic resonance imaging (mri) and more recently electron spin resonance imaging (esri).