HETEROCYCLES
An International Journal for Reviews and Communications in Heterocyclic ChemistryWeb Edition ISSN: 1881-0942
Published online by The Japan Institute of Heterocyclic Chemistry
Special Issue
Tetsuji Kametani's Special Issues, Vol. 30, No. 1, 1990
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■ A Unique Transformation of 5-Amino-N’-methoxyimidazole-4-carboxamidines by Diazotization: Synthesis of the 5-Azido Analogue of ACIA Riboside
Tohru Saito, Yayoi Asahi, Satoshi Nakajima, and Tozo Fujii*
*Faculty of Pharmaceutical Scicences, Kanazawa University, 13-1 Takara-machi, Kanazawa 920-0934, Japan
Abstract
Diazotization of 1-substituted 5-amino-N’-methoxyimidazole-4-carboxamidines (I) was found to give the 5-azidoimidazole-4-carbonitriles II through the 1-methoxy-2-azaadenine intermediates IV. The product IIb from the riboside Ib was utilized for the synthesis of 5-azido-1-β-D-ribofuranosylimidazole-4-carboxamide (Vb), a novel AICA riboside analogue.
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■ A Stereoselective Synthesis of (2Z,4E)-Dienoic Acid Involving Masked Functional Groups: n-Bu4NF Induced Ring-Opening of α,β-Unsaturated δ-Lactone
Tadashi Nakata,* Noriaki Hata, and Takeshi Oishi*
*The Institute of Physical and Chemical Research, Wako-shi, Saitama 351-0198, Japan
Abstract
n-Bu4NF induced ring-opening of α,β-unsaturated δ-lactone produced (2Z,4E)-dienoic acid without affecting acetoxyl groups present in the side chain of the lactone ring.
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■ A New Synthesi of (±)-Chilenamine, an Isoindolobenzazepine Alkaloid
Shingo Yasuda, Yu-ichi Sugimoto, Chisato Mukai, and Miyoji Hanaoka*
*Faculty of Pharmaceutical Scicences, Kanazawa University, 13-1 Takara-machi, Kanazawa 920-0934, Japan
Abstract
(±)-Chilenamine (1), an isoindolobenzazepine alkaloid, was efficiently synthesized starting from 6-bromo-2,3-dimethoxybenzaldehyde (5) and 3,4-methylenedioxyphenethylamine (6) via the N-substituted benzazepine (10) by radical cyclization.
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■ An Asymmetric Synthesis of the Takano Lactone. A Formal Synthesis of 9-(—)-Eburnamine
A. I. Meyers,* Jeffery Romine, and Albert J. Robichaud
*Department of Chemistry, Colorado State University, Fort Collins, CO 80523-1872, U.S.A.
Abstract
The lactone 2 known as a precursor to the alkaloid eburnamine 1 has been prepared via bicyclic lactam 4 in 4 steps in 35% overall yield and >99% enantiomeric excess.
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■ Stereoselective Epoxydation of 1-Iridene Derivatives. Total Syntheses of Methyl Chokolate A and Matatabiether
Nobuo Kato,* Masashi Kamitamari, Shoji Naganuma, Hiroaki Arita, and Hitoshi Takeshita*
*Instituete of Advanced Material Study, Kyushu University, 6-1, Kasuga-koen, Kasuga 816-8580, Japan
Abstract
Sharpless oxidation of 1-iridenes stereoselectively afforded trans-epoxy derivatives. As expected, the selectivity was inversed to give cis-epoxy derivatives when 1-iriden-9-ols were similarly treated. The trans- and cis-epoxy derivatives, thus obtained, were converted into optically active methyl chokolate A and matatabiether, respectively.
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■ Reaction of Triheteroarylphosphines with Organolithium Reagents Concurrent Ligand Exchange and Ligand Coupling
Yuzuru Uchida,* Yoshikazu Takaya, and Shigeru Oae*
*Department of Applied Chemistry, Osaka Institute of Technology, Asahi-ku,Osaka, Osaka 535, Japan
Abstract
Reaction of tri(2-benzothiazyl)phosphine or tri(2-pyridyl)phosphine with aryl- or heteroaryllithium compounds in THF affords 2,2’-bibenzothiazyl or 2,2’-bipyridyl by ligand coupling in good yields.
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■ Preparation of Optically Acyive 1,3,2-Oxathiaphosphorinanes Using (-)-10-Mercaptoisoborneol as a Chiral Source
Tamiko Takahashi, Makoto Matsui, Naoko Maeno,* Toru Koizumi,* and Motoo Shiro
*Faculty of Pharmaceutical Sciences, Toyama Medical and Pharmaceutical University, 2630 Sugitani, Toyama, Toyama 930-0194, Japan
Abstract
Optically active 1,3,2-oxathiaphosphorinanes (3) and (4) were prepared from (-)-10-mercaptoisoborneol (1) and phosphorus dichlorides [RP(X)Cl2] (2). The configuration at phosphorus in these derivatives was assigned on the basis of their 1H nmr spectral data and X-ray diffraction analysis of 4f.
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■ High Pressure Diels-Alder Reaction of 1-Methyl-2(1H)-pyridones Having a Phenyl Group with N-Phenylmaleimide
Hiroshi Tomisawa,* Hiroto Nakano, and Hiroshi Hongo
*Tohoku Pharmaceutical University, 4-4-1 Komatsushima, Aoba-ku, Sendai 981-8558, Japan
Abstract
Diels-Alder reaction of 1-methyl-2(1H)-pyridones (Ia-d) having a phenyl group at 3,4,5, and 6 position with N-phenylmaleimide (II) under 10 kbar at 110°C for 72 h gave a mixture of the endo and exo adducts (IIIa-d and IVa-d) in good yields, some of which were unobtainable under atmospheric pressure conditions.
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■ An Efficient Synthesis of Natural (+)-Neoisostegane Using Asymmetric Hydrogenation Catalyzed by a Chiral Bisphosphine-Rhodium(I) Complex
Toshiaki Morimoto, Mitsuo Chiba, and Kazuo Achiwa*
*Schol of Pharmaceutical Sciences, University of Shizuoka, 52-1 Yada, Shizuoka 422-8526, Japan
Abstract
(+)-Neoisostegane, a natural lignan lactone was synthesized by utilizing a catalytic asymmetric hydrogenation of α-veratrylidenesuccinic acid half-ester with a (S,S)-MOD-DIOP-rhodium(I) as a key step, and the absolute configuration was determined to be (M,6R,7R).
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■ N3-(Arylthio-, Aralkylthio- and Alkylthio)-5,5-dimethylhydantoins: Sulfenyl Group Transfer Reactions and Their Propertied
Ken’ichi Takeda* and Kusuo Horiki
*Shionogi Research Laboratories, Shionogi & Co. Ltd., Fukushima-ku, Osaka 553-0002, Japan
Abstract
Sulfenyl-transfer reactions toward a variety of nucleophiles were successfully carried out using N3-sulfenyl-substituted 5,5-dimethylhydanations (2a-c). During the course of the synthesis of 2 by the reaction of N1-bromo-5,5-dimethylhydantoin (1c) with disulfides, the sulfenyl groups were found to be at the position of N3 although the bromine was at N1 in the starting monobromohydantoin (1c). Some mechanistic speculations were considerd for the formation of 2 and 1c.
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■ New Method and Reagents in Organic Synthesis. 87. Reaction of Trimethylsilyldiazomethane with Quinones
Toyohiko Aoyama,* Takao Nakano, Satoshi Nishigaki, and Takayuki Shioiri*
*Faculty of Pharmaceutical Sciences, Nagoya City University, Tanabe-dori, Mizuho-ku, Nagoya 467-8603, Japan
Abstract
Reaction of trimethylsilyldiazomethane with various quinones affords indazoles 2, 2-substituted 3-trimetylsilylmethyl-1,4-quinones 3, silylcyclopropanes 4, and trimethylsilylmethylenedioxy derivatives 5, depending upon substrates.
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■ Chiral Synthesis of the Intermediate of Atisine
Masataka Ihara, Makoto Suzuki, and Keiichiro Fukumoto*
*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan
Abstract
The chiral key intermediate, (+)-(1R,5R)-3-benzyl-1-methoxymethyloxymethyl-5-methyl-9-methylene-3-azabicyclo[3.3.1]nonane (2), for the synthesis of atisine (5) was prepared from dimethyl 3-benzyl-3-azabicyclo[3.3.1]nonan-9-one-1,5-dicarboxylate (6) by a chemical methodology.
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■ Formation of Morphinandienones via o-Quinol Acetates of N-Trifluoroacetyltetrahydroisoquinolin-7-ols
Osamu Hoshino,* Hiromichi Ogasawara, Masaji Suzuki, Minoru Arasawa, and Bunsuke Umezawa
*Faculty of Pharmaceutical Sciences, Science University of Tokyo, 2641 Yamazaki, Noda, Chiba 278-8510, Japan
Abstract
(±)-N-Trifluoroacetylnormorphinandienones (4a,b) were obtained by acid treatment of o-quinol acetates [o-QAs] (2a,b) in CH2Cl2 or CH3CN at low temperature.
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■ (18-Crown-6)-linked Binuclear Phthalocyanines
Nagao Kobayashi,* Marcin Opallo, and Tetsuo Osa*
*Graduate School of Pharmaceutical Sciences, Tohoku University, Aramaki, Aoba-ku, sendai 980-8578, Japan
Abstract
(18-Crown-6)-linked binuclear phthalocyanines have been synthesized and their electronic absorption and magnetic circular dichroism spectra have been recorded. Neither alkaline nor alkaline earth metals have affected the spectra.
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■ Amino Acids as Synthons for Heterocycles. Formation of 1,2,4-Triazine Derivatives
Janes Smodis, Rok Zupet, Andrej Petric, Branko Stanovnik, and Miha Tisler*
*Department of Chemistry and Chemical Technology, E. Kardelj University, Murnikova 6, 61000 Ljubljana, Slovenia
Abstract
Transformation of the amino group of amino acids into an amidine and subsequent treatment with hydrazine leads to 1,2,4-triazine-6(1H)-ones. The method described is a new synthetic approach. Unsaturated amino acids gave imidazol-5-one derivatives after the same reaction sequence.
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■ Carbon Dioxide: A Reagent for the Simutaneous Protection of Nucleophilic Centers and the Activation of Alternative Locations to Electrophlic Attack. 16. A Novel Synthetic Method for the Side-Chain Functionalization of N-Methyl-o-toluidine and for the Preparation of 2-Substitiuted N-Methylindoles
Alan R. Katritzky,* Wei-Qiang Fan, Kunihiko Akutagawa, and Jin Wang
*Center for Drug Discovery, College of Pharmacy, University of Florida, Gainesville, Florida 32611-7200, U.S.A.
Abstract
N-Methyl-o-toluidine is readily converted into a range of side-chain functionalized derivatives in a one-pot sequence, using carbon dioside for N-protection. The intermediate lithium carbamate is futher lithiated by butyllithium at the side chain methyl group, and then reacted with an electrophile; the product undrergoes acid-catalyzed decarboxylation during work-up. 2-Substituted N-methylindoles are produced when carboxylate esters are used as electrophiles. The yields are good, and no ring-substituted products are detected.
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■ The Synthesis of 9-(1-Azetidinyl)-1,2,3,4-tetrahydroacridine
Eric. T. Michalson, Stan D’Andrea, Jeremiah P. Freeman, and Jacob Szmuszkovicz*
*Department of Chemistry, University of Notre Dame, Notre Dame, IN 46556, U.S.A.
Abstract
Synthesis of analogue (2) of tacrine is described in which the primary amino group is replaced by the azetidine moiety. The synthesis was accomplished in two steps from the acridinone derivative 10. This involved conversion of 10 to triflate 11, followed by treatment with azetidine to give the target compound 2.
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■ A Facile Synthesis of 3-(2-Amino-4-ethoxyphenyl)pyridine
Kimiyuki Shibuya, Hiromichi Shigyo, and Tomio Ohta*
*Tokyo Research Laboratories, Kowa Co., Ltd., 2-17-43, Noguchi-cho, Higashimurayama 189, Japan
Abstract
A facile and efficient synthesis of 3-(2-amino-4-ethoxyphenyl)pyridine (6), a key intermediate of the antiarrythmic agent, has been developed starting from 3-bromopyridine (2) by the benzyne reaction using sodium benzylamide as the key step.
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■ Purines. IX. Reaction of 9-Phenyl-9H-purine-2-carbonitriles with Grignard Reagents
Ken-ichi Tanji* and Takeo Higashino
*Laboratory of Organic Chemistry, School of Food and Nutritional Sciences, University of Shizuoka, 52-1 Yada, Shizuoka 422-8526, Japan
Abstract
The palladium-catalyzed cross-coupling reaction of 2- and 6-chloro-9-phenyl-9H-purines with potassium cyanide proceeded to give 9-phenyl-9H-purine-2- (3a-c) and -6-carbonitriles (4a-c). The conversion of the cyano group at the 2-position into the corresponding acyl group was achieved by treatment of 3a,b with Grignard reagents.
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■ Structures of Elaeodendrosides M, N, O P, Q, R and S. A Series of Cardiac Glycosides Isolated from Elaeodendron glaucum
Kazutake Shimada,* Hiroshi Masuda, Hiroshi Ohtaki, Norihiko Kobayashi, and Toshio Nambara
*Faculty of Pharmaceutical Scicences, Kanazawa University, 13-1 Takara-machi, Kanazawa 920-0934, Japan
Abstract
Seven cardiac glycosides having an unusual sugar linkage, elaeodendrosides M, N, O, P, Q, R and S, were isolated from seeds of Elaeodendron glaucum.
These were unequivocally characterized on the basis of physical data and chemical correlation with related compounds previously isolated. These new compounds were tested for inhibitation of Na+, K+-adenosine triphosphatase from guinea pig heart, and the structure-activity relationships has been discussed.
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■ The Nicholas Reaction of Indoles. Propargylation of Indoles with (Propargyl)dicobalt Hexacarbonyl Cations
Masako Nakagawa,* Jian Ma, and Tohru Hino*
*Faculty of Pharmaceutical Sciences, Chiba University, 1-33 Yayoi-cho, Inage-ku, Chiba 263-8522, Japan
Abstract
Indole reacted with (propargyl alcohol)Co2(CO)6 complex 1 to give 3-(1,1-dimethylpropargyl)indole 3, whereas N’-methoxycarbonyltryptamine 7 gave the corresponding N-substituted derivative 11. The reaction of 7 with (propargyl acetate)Co2(CO)6 complex 23 provided 3a-(1,1-dimethylpropargyl)hexahydropyrroloimidole cobalt complex 9. Oxidative demetalation of 3, 11, and 9 with Fe(NO3)3 gave 5, 13, and 27, respectively. Hydrogenation of 5 afforded the corresponding 3-(1,1-dimethylallyl)indole 6.
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■ Synthesis of N, N’-Bis(aryl)-N-(2-thiazolin-2-yl)thioureas
M. Avalos González, R. Babiano Caballero, P. Cintas Moreno,* J. L. Jiménez Requejo, and J. C. Palacios Albarrán
*Department of Organic Chemistry, Facultad de Veterinard, University of Extremadura, 06071-Badajoz, Spain
Abstract
The reaction of arylisothiocyanates with 2-chloroethylamine in pyridine led to the formation of complex N,N’-bis(aryl)-N-(2-thiazolin-2-yl)thioureas (1-3). These compounds and the mixed thioureas or ureas 8-11, show a strong chelated structure due to the presence of an intramolecular hydrogen bond.
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■ Synthesis of 2-Substituted Drivatives of Diltiazem
Masamichi Morimoto, Harumichi Kohno, Kosuke Yasuda, Tadamasa Date, Norio Takamura,* and Shigehiko Sugasawa
*Discovery Research Laboratory, Tanabe Seiyaka Co. Ltd., 2-2-50, Kawagishi, Toddda, Saitama 335-8505, Japan
Abstract
Titled compounds, 2a,b,c,d and e, were efficiently synthesized from 3-acetoxy-2-(4-methoxyphenyl)-1,5-benzothiazepin-4(5H)-one (4) through alkylation at the C2-position followed by stereoselective reduction of the C3-carbonyl group.
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■ Lithiated 2-Methyl-5-Phenyloxizoles, Formation and Reactions with Electrophiles
Choji Kashima,* Hideki Arao, and Rieko Okada
*Department of Chemistry, University of Tsukuba, 1-1-1 Ten-nodai, Tsukuba-shi, Ibaraki, 305-8571, Japan
Abstract
The methyl group of 2-methyl-5-phenyloxazole (1) has been lithiated with lithium diisopropylamide (LDA) and the resulting lithio derivative has been reacted with electrophiles to obtain 2-alkyl-5-phenyloxazoles.
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■ Photochemical Reactions of 4-Phenylquinazolin-2-ones
Takehiko Nishio,* Satoshi Kameyama, Yoshimori Omote, and Choji Kashima
*Department of Chemistry, University of Tsukuba, 1-1-1 Ten-nodai, Tsukuba-shi, Ibaraki, 305-8571, Japan
Abstract
Irradation of 4-phenylquinazolin-2-ones (1) in the presence of hydrogen donor such as xanthene (2a), sulfide (2c), and acylic or cyclic ethers (2b,d-e), gave the C-C bonded 1:1-adducts of (1) and (2) via hydrogen atom abstraction of the excited imino nitrogen of (1), while irradiation of (1) in the presence of triethylamine gave the reduced 3,4-dihydroquinazolin-2-ones.
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■ N-Acyliminium Cyclizations: Formation of the Furo[3,4-a]pyrrolizine Ring System
Hugo Ent, Henk de Koning, and W. Nico Speckamp*
*Organic Chemistry Department, University of Amsterdam, Nieuwe Achtergracht 129, 1018 WS Amsterdam, The Netherlands
Abstract
The hydroxylactams 5a,b could be converted into the furo[3,4-a]pyrrolizine derivatives 10a,b via the 2-aza-Cope rearrangement cyclization of N-acyliminium ions.
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■ Novel Epidithiodioxopiperazines, Emethallicins E and F, from Emericella heterothallica
Nobuo Kawahara, Koohei Nozawa, Mikio Yamazaki, Shoichi Nakajima, and Ken-ichi Kawai*
*Hoshi University, 2-4-41 Ebara, Shinagawa-ku, Tokyo 142-8501, Japan
Abstract
Novel epidithiodioxopiperazines, emethallicins E (1) and F (2), were isolated from the mycelial extract of Emericella heterothallica (mating type A). The structures of emethallicins E (1) and F (2) were determined on the basis of spectroscopic and chemical investigation, compared with other emethallicins isolated from the above fungus and the other strain. Emethallicin E (1) is an epidithiodioxopiperazine having a novel carbon skeleton related to emethallicins A (3), B (4), C (5), and D (6), whereas emethallicin F (2) and D (6). Emethallicins E (1) and F (2) have a potent inhibitory activity for histamine release as well as the other emethallicins.
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■ Palladium(0) Catalyzes Reactions of 1,4-Epiperoxides
Masaaki Suzuki, Yoshihisa Oda, Nobuyuki Hamanaka, and Ryoji Noyori*
*Department of Chmistry, Graduate School of Science, Nagoya University, Chikusa, Nagoya, Aichi 464-8601, Japan
Abstract
The Pd(PPh3)4 catalyzed reaction of 2,3-saturated and 2,3-unsaturated 1,4-epiperoxides proceeds by courses markedly different from those of the previously reported transition metal catalyses. The pd(0)-promoted reaction of 2,3-saturated epiperoxides gives the corresponding 4-hydroxy ketones and 1,4-diols as the major products. From 2,3-dedihydroepiperoxides are formed the corresponding 4-hydroxy enones, syn-1,2:3,4-diepoxides, and 1,4-diols. The results are interpreted in terms of competing Pd(0)/Pd(II) and Pd(0)/Pd(I) exchange mechanisms. Exposure of prostaglandin (PG) H2 methyl ester to Pd(PPh3)4 produces a mixture of methyl esters of PGD2, PGE2, PFF2α, and (5Z,8E,10E,12S)-12-hydroxy-5,8,10-heptadecatrienoic acid.
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■ Tashiromine; a New Alkaloid from Maackia tashiroi
Shigeru Ohmiya,* Hajime Kubo, Hirotaka Otomasu, Kazuki Saito, and Isamu Murakoshi
*Institute of Medicinal Chemistry, Hoshi University, 2-4-41 Ebara, Shinagawa-ku, Tokyo 142-8501, Japan
Abstract
A new alkaloids (1) containing an indolizidine ring, named tashiromine, was isolated from the stems of Maackia tashiroi (Leguminosae) together with seven lupin alkaliods and ammodendrine. The structure of 1 was determined as (5S,6R)-5-hydroxymethyl-trans-indolizidine or its enantiomer by comparison of the spectral data with those of the synthetic diastereomers of 5-hydroxymethly-trans-indolizidine.
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■ A 31P NMR Study of Reactions of 2,3-Bis(diohenylphosphino)-6-phenyl-λ3-phosphinine with Sulfer: Formation, Characterization, and Further Reaction of a Stable Phosphinine 1-Sulfide
Alan N. Hughes* and Karen L. Knudsen
*Department of Chemistry, Lakehead University, Thunder Bay, Ontario, P7B 5E1, Canada
Abstract
The reactions of 2,3-bis(diphenylphosphino)-6-phenyl-λ3-phosphinine with sulfer at room temperature and at elevated temperatures are discussed. Among the products formed is 2-diphenylphosphino-3-diphenylthiophosphinyl-6-phenylphosphinine 1-sulfide, a rare example of a relatively stable heterocycle containing σ3λ5 phosphorus. The route whereby this is formed and its subsequent reaction with traces of H2S slowly generated in the reaction medium are also discussed in the light of nmr evidence.