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. 43, No. 12, 1996
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■ New Syntheses of Benzotriazepines by Non-convenient Cyclization Reaction of N1,N3-Diarylamidrazones
Petra Frohberg and Peter Nuhn*
*Institute of Pharmaceutical Chemistry, Martin-Luther-University Halle-Wittenberg, Wofgang-Langenbeck-Str. 4, 06120 Halle, Germany
Abstract
Reactions od derivatives of amidrazones with formaldehyde give triazole, triazoline and unexpected benzotriazepine derivatives. we examined the effects of the substitution pattern of the N3-Aryl ring.
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■ Synthesis of (-)-Vertinolide
Keizo Matsuo* and Yusuke Sakaguchi
*Faculty of Pharmaceutical Sciences, Kinki University, 3-4-1, Kowakae, Higashi-Osaka 577-8502, Japan
Abstract
(-)-Vertinolide, a β-tetronic acud derivative isolated from Verticillium intertextum as one of the mycotoxins, was synthesized starting from (R)-lactic acid as the chiral source using Seebach’s chiral self-reproduction method.
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■ Asymmetric Synthesis of (S)-Norlaudanosine and (S)-Tetrahydrohomopapaverine by Catalytic Asymmetric Hydrogenation with Chiral Diphosphine-Iridium(I)-Phthalimide Complex Catalysts
Toshiaki Morimoto,* Naoaki Suzuki, and Kazuo Achiwa
*Schol of Pharmaceutical Sciences, University of Shizuoka, 52-1 Yada, Shizuoka 422-8526, Japan
Abstract
Optically active 1,2,3,4-tetrahydroisoquinoline alkaloids, (S)-norlaudanosine and (S)-tetrahydrohomopapaverine, were prepared by catalytic asymmetric hydrogenation of 1-substituted 3,4-dihydro-6,7-dimethoxyisoquinolines with 1 mol % of an iridium(I) complex of (2S,4S)-BCPM or (S)-BINAP in the presence of a phthalimide. Enantioselectivitis of up to 88% ee were attained.
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■ Formation of Dihydrobenzoxanthone Skeleton from 3-Isoprenylated 2',4',5'-Trioxygenated Flavone
Miwa Aida, Yukiko Yamagami, Yoshio Hano, and Taro Nomura*
*Faculty of Pharmaceutical Sciences, Toho University, 2-2-1, Miyama, Funabashi, Chiba 274-8510, Japan
Abstract
Photoreaction of artonin E (1), 3-isoprenylated 2’,4’,5’-trioxygenated flavone, produced artobiloxanthone (2) and cycloatrobiloxanthone (3). Furthermore, the treatment of artonin E (1) with a radical reagent (DPPH) resulted in the same products. These finding support that the flavone derivatives having the dihydrobenzoxanthone skeleton are biogenetically derived from the 3-isoprenylated 2’,4’,5’-trioxygenated flavones through the phenol oxidative cyclization.
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■ Synthesis of Dibenzo[d,f]-1,2-selena and -1,2-thiazepin-3-ones Derivatives, Bis-homo-ebselen
Abdelaziz Mohsine* and Léon Christiaens
*Université de Liège, Chimie Organique Hétérocyclique, Institut de chimie, Bat. B6. Sart Tilman 4000 Liège, Belgium
Abstract
Dibenzo[d,f]-1,2-selena and -1,2-thiazepin-3-ones derivatives were prepared from the corresponding 2-alkylselanyl- and 2-alkylsulfanylbiphenyl-2’-carboxamides or their diselenide or disulfide derivatives. These new seven-membered seleno-compounds are homologues of Ebselen (PZ51) (1) which exhibits glutathion peroxidase activity. Bis-homologues of PZ25 (2) were also synthesized. Synthesis of benzo[c]selenocoumarin via a directed ortho metalationbolonic acid cross-coupling reaction and it’s ring-opening reaction are the first step of the synthetic pathway.
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■ Stereospecific Approaches to C-12 Substituted Pyrrolo[1',2':2,3]pyridazino[6,1-a]isoindolones
Stefan Marchalin and Bernard Decroix
*Laboratoire de Chimie, Faculté des Sciences et Techniques, Université du Havre, 25, rue Philippe Lebon, BP 540, 76600 Le Havre Cedex, France
Abstract
Isomerization of the cis-alcohol (2) to the trans-alcohol (3) was achieved by treatment with sodium ethoxide in ethanol solution. Various trans-C12 substituted productss (5-10) are prepared from alcohols (2), (3). On the other hand, cis-N,N-dimethylamino compound (14) was obtained in a three steps sequence from the acetic derivative (11).
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■ Synthesis and Rearrangement of 6H-Imidazo[1,2-c]quinazolin-5-ones
Wolf Arnold, Bernd Büttelmann,* Marie-Paule Heitz, and René Wyler
*Pharma Division, Pharma Preclinical Research & Development, F.Hoffmann-La Roche Ltd., Grenzacherstrasse 124, CH-4070 Basel, Switzerland
Abstract
The synthesis of new substituted 6H-imidazo[1,2-c]quinazolin-5-ones (2) is described. 3-Substituted 6H-imidazo[1,2-c]quinazolin-5-ones (3) undergo a Dimroth-type rearrangement to the thermodynamically more stable 2-substituted 6H-imidazo[1,2-c]quinazolin-5-ones (4).
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■ An Access to Optically Active Carbacephems
Saïd Oumoch and Gérard Rousseau*
*Laboratoire des Carbocycles, Associé au CNRS, Institut de Chimie Moleculaire d'Orsay, Bat. 420, Université de Paris-Sud, 91405 Orsay Cedex, France
Abstract
Optically active 4-allyl-1-hydroxymethylazetidin-2-ones (1) (R = H, Ph, CH2CO2Me,CH2Sph; R’ = H, R = CO2Me; R’ = Me) have been obtained by enzymatic transesterification with vunyl acetate in the presence of the lipase from Pseudomonas cepacia. These compounds were either transformed into chiral carbacephems (R = Ph, CH2CO2Me) by reaction with Lewis acids or into N-methoxycarbonylhydroxymethyllactam (11c) (R = CH2CO2Me). Lactam (11c) was then transformed into the corresponding optically active carbacepham (17) or after chemical transformation into optically active carbacephem (18).
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■ Synthesis and Pharmacological Activity of Metabolites of Vasopressin V1 Receptor Antagonist, OPC-21268
Kenji Otsubo, Jun Matsubara, Tadaaki Ohtani, Yoshikazu Kawano, Kazuyoshi Kitano, Seiji Morita, Kazumi Kondo, Yoshitaka Yamamura, and Minoru Uchida
*Tokushima Research Institute, Otsuka Pharmaceutical Co., Ltd., Kagasuno 463-10, Kawauchi-cho, Tokushima, Tokushima 771-0192, Japan
Abstract
The metabolites of 1-[1-[4-(3-acetylaminopropoxy)benzoyl]-4-piperid-yl]-3,4-dihydro-2(1H)-quinolinone (OPC-21268, 1), vasopressin V1 receptor antagonis were synthsized to confirm the proposed structures and to examine their vasopressin V1 receptor antagonistic activity. The structures of methabolites (2a-6) were identified by means of comparison with synthetic compounds. The activity of the metabolites was found to be lower that that of 1.
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■ Cycloaddition of Acetylenes with 5-Azido-5-deoxy-D-aldopentose Derivatives: Synthesis of Triazole Reversed Nucleoside Analogs
Peter Norris, Derek Horton,* and Brett R. Levine
*Department of Chemistry, The American University, 4400 Massachusetts Avenue N.W., Washington, D.C. 20016-8014, U.S.A.
Abstract
1,3-Dipolar cycloadditions of 5-azido-5-deoxy-1,2-O-isopropylidene-α-D-xylofuranose (1) or methyl 5-azido-5-deoxy-2,3-O-isopropylidene-β-D-ribofuranoside (4) with various acetylenes lead in most cases to mixtures of isomeric triazoles, the C-4 substituted product predominating in each case. The D-xylose derivatives (10) and D-ribose derivatives (12) were used as precursors to reversed analogs (16) and (17).
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■ New Synthetic Route to of 1,2,4-Thiadiazolines and 1,3-Thiazolines via Thiadiazolopyridinium Salts
Ana Martinez,* Ana Castro, Isabel Fonseca, Martin Martinez-Ripoll, Félix H. Cano, and Armando Albert
*Instituto de Química Médica, C. S. I. C., Calle Juan de Cierva, 3, 28006 Madrid, Spain
Abstract
A new efficient synthesis of 1,2,4-thiadiazolidines and 1,3-thiazolidines bearing 2-pyridylimino substituents using thiazolopyridinium chlorides as intermediates is described. The mechanism probably involves a base promoted nucleophilic addition of thiazolopyridinium salts to nitriles and ketones.
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■ Synthesis and Reactivity of N-Diphenylphosphinoyltroponimine: Synthetic Entry into 1-Azaazulene Derivatives
Tohru Takayasu, Koji Ito, and Makoto Nitta*
*Department of Chemistry, School of Science and Engineering, Waseda University, 3-4-1 Okubo, Shinjuku-ku, Tokyo 169-8555, Japan
Abstract
A novel N-diphenylphosphinoyltroponimine (5), which is highly polarized and has a low lying LUMO, was prepared. The ateempted reaction of 5 with wnolate ions and enamines derived from cyclic ketones gave 1-azaazulene derivatives, albeit in low yields.
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■ Selenium Catalyzed Conversion of δ-Phenyl-γ-alkenyl Oximes into 2-Phenylpyridines
Marcello Tiecco,* Lorenzo Testaferri, Luana Bagnoli, Francesca Marini, Claudio Santi, and Andrea Temperini
*Istituto di Chimica Organica, Facoltà di Farmacia, Università degli Studi di Perugia, Via del Liceo 1 06123-Perugia, Italy
Abstract
δ-Phenyl-γ-alkenyl oximes react with an excess of ammonium persulfate and catalytic amounts of diphenyl diselenide in the presence of trifluoromethanesulfonic acid in acetonitrile to afford 2-phenylpyridines and 2-phenylpyridine N-oxides in moderate yields.
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■ Synthesis and Biological Evaluation of 3-Hydroxymethylpyrimido[1,6-c][1,3]oxazine Derivatives
Ling-Yih Hsu* and Chung-Hsun Lin
*School of Pharmacy, National Defense Medical Center, P.O. Box 90048-508, Neihu, Taipei, Taiwan, R.O.C.
Abstract
A number of 5-substituted 3-hydroxymethylpyrimido[1,6-c][1,3]oxazine derivatives were synthesized and evaluated for their biological activity. Compound (10) showed slight activity (GI50 = 2.7 μM) against MDA-MB-231/ATTC Breast cancer cell line.
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■ Practical Synthesis of 1H-Indazole-3-carboxylic Acid and Its Derivatives
Toyokichi Yoshida,* Noriyasu Matsuura, Katsuhisa Yamamoto, Masahiro Doi, Kanji Shimada, Toshiya Morie, and Shiro Kato
*Technical Research Laboratory, Dainippon Pharmaceutical Co., LTD., Ebie 1-5-51, Fukushima-ku, Osaka 553, Japan
Abstract
A practical and convenient synthesis of 1H-indazole-3-carboxylic acid and its amide and ester derivatives from the corresponding derivatives of 2-nitrophenylacetic acid was described.
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■ Synthesis of h6-(Octahydroacridine)chromiumtricarbonyl Complexes with Non-polar Tails via Molecular Sieves-Catalyzed Cyclization of N-Arylimines and Subsequent Diastereoselective Complexation
Jörg L. Schulte, Sabine Laschat,* Sirpa Kotila, Jürgen Hecht, Roland Fröhlich, and Birgit Wibbeling
*Organisch-Chemisches Institut, Westfälische Wihelms-Universität Münster, Corrensstrasse 40, D-48149 Münster, Germany
Abstract
Molecular sieves catalyzed cyclization of both various N-arylimines formed in situ from the corresponding arylamines and 3,3,7-trimethyl-6-octenal yielded trans-condigurated octahydroacridines. After attachment of non-polar alkyl chains these heterocycles can be complexed diastereoselectively to Cr(CO)3. The products were characterized by X-ray crystal structure determination.
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■ Stereoselective Synthesis of (Z)-α-Alkylidene-γ-butyrolactone from 2-Alkyn-1-one
Fen-Tair Luo,* May-Wen Wang, and Yi-Show Liu
*Institutue of Chemistry, Academia Sinica, Nankang, Taipei,11529, Taiwan, R.O.C.
Abstract
A preparation of (Z)-α-alkylidene-γ-butyroactone with or without alkyl or aryl substituent at γ-position from 2-alkyn-1-one is provided.
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■ Synthesis of 5-Arylamino-3-arylimino-1,2-dithiole-4-sulfonamides from Methanesulfonamides and Aryl Isothiocyanates
Masahiko Takahashi* and Shinzi Yoshizawa
*Department of Materials Sciences, Faculty of Engineering, Ibaraki University, 4-12-1 Nakanarusawamachi, Hitachi, Ibaraki 316-8511, Japan
Abstract
5-Arylamino-3-arylimino-1,2-dithiole-4-sulfonamides were obtained in one pot by the reaction of methanesulfonamides with aryl isothiocyanates in the presence of butyllithium followed by oxidation with hydrogen peroxide.
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■ A Concise Synthesis of 7-Substituted Indoles
Yoshinori Kondo, Satoshi Kojima, and Takao Sakamoto*
*Faculty of Pharmaceutical Sciences, Tohoku University, Aramaki, Aoba-ku, sendai 980-8578, Japan
Abstract
7-Substituted indoles were synthsized by the vasic cyclization of 6-substituted tert-butyl 2-(trimethylsilylethynyl)phenylcarbamates which were derived by the lithiation of tert-butyl 2-(trimethylsilylethynyl)phenylcarbamate and the subsequent reaction with electrophiles.
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■ Structure Elucidation and Synthesis of a Metabolite of Antiinflammatory Drug DUP 697
Shizuo Nakamura, Mitsuyoshi Kondo, Kiyoto Goto, Mitsuhiro Nakamura, Yoshiaki Tsuda, and Kozo Shishido*
*Institute for Medicinal Resources, University of Tokushima, Sho-machi, Tokushima 770-8505, Japan
Abstract
Structure of the O-glucuronide (2), one of the metabolites of antiinflammatory drug DUP 697 (1), has been elucidated on the basis of spectral data and a total synthesis of it has been accomplished. Since the synthetic route to 2 is an unambiguous one, complection of the synthesis established the assigned sturcture.