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. 29, No. 11, 1989
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■ Chemoselective Reduction of Lactams to Teritary Amines Using Tributylyin Hydride
Jean-Yves Laronzo,* Brigitte Guilleteau, Dominique Cartier, Jacquwline Laronze, and Jean Lévy
*Laboratoire de Transformation et Syntheses deSubstances Naturelles, Faculté de Pharmacie, Université de Reims-Champagne-Ardenne, 51, rue Cognacq-Jay, F-51096 Reims Cedex, France
Abstract
The piperidone carbonyl in the tetracyclic oxindolic derivatives (1a-d) was chemoselectively deoxygenated in good to fair yields by reacting the derived alkylthioiminiums (3a-d) with tributyltin hydride.
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■ The Synthesis of Eudistomins S and T: β-carbolines from the Tunicate Eudistoma olivaceum
Ian W. J. Still* and James McNulty
* J. Tuzo Wilson research Laboratories, Erindale Campus, University of Toronto in Mississauga, Mississauga, Ontario, L5L 1C6, Canada
Abstract
The syntheses of two β-crbolines, eudistomins S and T, have been accomplished from tryptamine precursors.
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■ Enzyme-mediated Acylation of Flavonoid Monoglycosides
Bruno Danieli,* Paolo De Bellis, Giacomo Carrea, and Sergio Riva*
*Dipartimento di Chimica Organica e Industriale, Centro C. N. R., Università degli Studi di Milano, V. Venezian 21, I-20133 Milano, Italy
Abstract
Subtilisin catalyzes the reaction of the flavonoid glucosides 1 and 3 with trifluoroethyl butanoate (CH3CH2CH2COOCH2CF3) in pyridine to afford the corresponding 3”-O-mono-, 6”-O-mono-, and 3”,6”-O-diacyl derivatives, while the rhamnoside 2 is unaffected.
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■ Enantioselective Addition of Dialkylzincs to Pyridinecarbaldehyde in the Presence of Chiral Aminoalcohols: Asymmetric Synthesis of Pyridylalkyl Alcohols
Kenso Soai,* Hiroshi Hori, and Seiji Niwa
*Department of Applied Chemistry, Faculty of Science, Science University of Tokyo, Kagurazaka 1-3, Shinjuku-ku, Tokyo 162-8601, Japan
Abstract
1-(3-Pyridyl)ethanol and -propanol were synthesized in moderate to good enantiomeric excesses by the enantioselective addition of dialkylzincs to nicotinaldehyde using N,N-dibutylnorephedrine as chiral catalyst.
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■ A Stable Seven-membered Ring Ketene Imine from a Thiocarbonyl Ylide and an Acceptor Olefin
Rolf Huisgen,* Elke Langhals, Grzegorz Mloston, and Takumi Ohshima
*Institut für Organische Chemie, Universität München, Karlstrasse 23, D-80333 München, Germany
Abstract
2,2,4,4-Tetramethyl-3-thioxocyclobutanone S-methylide (2), generated from the 1,3,4-thiadiazoline 1 by N2 extrusion, combines with trans- and cis-1,2-dicyano-1,2-bis(trifluoromethyl)ethylene (7) furnishing nonstereospecifically five-membered thiolanes (8, 16) and a strained cyclic ketene imine in parallel reactions. The results of a mechanistic study are interpreted by zwitterionic intermediates.
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■ Ring Contraction of a Cyclic Seven-membered Ketene Imine
Rolf Huisgen,* Elke Langhals, and Takumi Ohshima
*Institut für Organische Chemie, Universität München, Karlstrasse 23, D-80333 München, Germany
Abstract
A cyclic ketene imine prepared from 2,2,4,4-tetramethyl-3-thioxocyclobutanone S-methylide and 2,3-bis(trifluoromethyl) fumaronitrile rearranges to the isomeric thiolane. The high dependence of the rate on solvent polarity and the steric course are in accordance with an open-chain zwitterionic intermediate.
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■ Versatile Synthesis of 5,6-Dihydro-1,4-dithiewpins and their Synthetic Applications
Kazuhiko Saigo,* Yukihiko Hashimoto, Lan Fang, and Masaki Hasegawa
*Department of Chemistry and Biotechnology, Graduate School of Engineering, University of Tokyo, Hongo, Bunkyo-ku, Tokyo 113-8656
Abstract
Readily available acyloin trimethylene dithioacetals rearranged in the presence of trimethylsilyl trifluoromethanesulfonate to give 5,6-dihydro-1,4-dithiepins. These compounds were converted to olefinic or acetylenic compounds using low valent metallic reductants.
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■ Synthesis of 3’-(1,2,3-Triazol-1-yl)-3’-deoxythymidines
Dieter Häbich,* Wolfgang Barth, and Manfred Rösner
*CWL-Pharma, Bayer AG, Postfach 10 17 09, 5600 Wuppertal-1, Germany
Abstract
The synthesis of various 3’-(1,2,3-triazol-l-yl)-3’-deoxythymidines 3 and their regioisomers 4 by 1,3-dipolar cycloaddition of AZT 1 with alkynes 2 is described.
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■ Ring Construction of Bicyclic γ-Lactams by Use of Electrochemical Oxidation
Miwako Mori,* Yumiko Watanabe, Katsuji Kagechika, and Masakatsu Shibasaki*
*Faculty of Pharmaceutical Sciences, Hokkaido University, Kita 12 Nishi 6, Kita-ku, Sapporo, Hokkaido 060-0812, Japan
Abstract
α-Acetoxy lactam derivatives generated from α-carboxy lactams by the use of electrochemical oxidation in the presence of AcONa in MeCN-AcOH were useful Intemediates for the synthesis of bicyclic lactams.
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■ Total Synthesis of the Pentacyclic Alkaloid Ascididemin
Franz Bracher*
*Institut für Pharmazeutische Chemie, Philipps-Universität, Marbacher Weg 6, D-35032 Marburg/Lahn, Germany
Abstract
The antileukemic alkaloid ascididemin (1) was prepared from quinoline-5,8-quinone (4) by oxidative amination with o-aminoacetophenone (5), followed by acid catalysed cyclisation and subsequent one pot annelation of ring E.
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■ Chemistry on Benzopentathiepin. Reactions of Benzopentathiepin with Active Methylene Compounds in the Presence of Base
Ryu Sato,* Yutaka Kanazawa, Yasuo Akutsu, and Minoru Saito
*Department of Applied Chemistry, Faculty of Engineering, Iwate University, 4-3-5 Ueda, Morioka, Iwate 020-8551, Japan
Abstract
Benzopentathiepin (BPT) reacted with various active methylene compounds such as malononitrile, ethyl cyanoacetate, ethyl acetoacetate, acetylacetone, ethyl 2-chloroacetoacetate, and ethyl α-chloropropionate in the presence of base such as triethylamine or sodium ethoxide to give dithiins, dithioles, or 1,2,4-trithiin in satisfactory yields.
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■ A Concise Enantio- and Stereocontrolled Synthesis of (+)-Ramulosin from (R)-O-Bezylglyidol
Seiichi Takano,* Youichi Shimazaki, and Kunio Ogasawara
*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan
Abstract
Ramulosin, a metabolite of Pestolatia ramulose, has been synthesized in enantio- and stereocontrolled fashion starting from (R)-O-benzylglycidol.
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■ Some Chemical Reactions of Taccalonoide A - a Bitter Substance from Tacca plantaginea
Zhong-liang Chen, Ji-hui Shen, and Yi-sheng Gao
*Academia Sinica, Shanghai Institute of Material medica, 319 Yue-yang Road, Shanghai 200031, China
Abstract
Taccalonolide A, a pentacyclic steroidal bitter principle from Chinese rnedicinal plant-Tacca plantaginea (Hance) Drenth, was studied by chemical reactions.
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■ Synthesis and Crystal Structure of Naphtho[2,1-b][1,5]naphthyridine
Isao Takeuchi, Yoshiki Hamada,* and Kimio Okamura
*Faculty of Pharmacy, Meijo University, 150 Yagotoyama, Tenpaku, Nagoya 468-8503, Japan
Abstract
A modified Skraup reaction was carried out on 2-aminobenzo-[f]quinoline (1), in the presence of sulfo-mix, using ferrous sulfate and boric acid. This reaction gave the linear type product, naphtho-[2,1-b][1,5]naphthyridine (2), but not the angular type. Its crystal structure was determined by X-ray analysis.
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■ Organogermanium Compounds; Spectrscopic Study on the Influence of Aryl Groups in the Organogermanium Aryl Compounds on the (p-d)π Interaction
Norihiko Kakimoto,* Katsuyuki Sato, Toyozo Takada, and Mitsuo Akiba*
*School of Pharmacy, Tokyo University of Pharmacy and Life Science, 1432-1 Horinouchi, Hachioji, Tokyo 192-0392, Japan
Abstract
The synthesis and properties of arylgermanium compounds through the reactions of aryllithium with germanium halides were investigated. 1H-Nmr spectroscopic analysis showed the (p-d)π interaction between the germanium atom and the double bond of the aryl group to diminish in the following group order: 2-benzofuranyl> 2-furanyl > 2-benzothiophenyl > 2-thiophenyl > phenyl group.
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■ Synthetic Applications of 2-(1,3-Dithian-2-yl)indoles. A New Synthetic Approach to Strychnos Alkaloids
Mario Rubiralta,* Antoni Torrens, Ignasi Reig, David S. Grierson, and Henri-Philippe Husson
*Laboratory of Organic Chemistry, Faculty of Pharmacy, University of Barcelona, Av. de Joan XXIII, s/n, 08028 Barcelona, Spain
Abstract
The first synthesis of Na-methyl-20-hydroxydasycarpidone 17b and the tetracyclic systems 16a and 16b are reported. The synthesis involves an acid cyclization of an appropriate 4-indolyl -carbonyl-2-piperidinecarbonitrile 15 which in turn is obtained
regioseiectively from the corresponding piperidinol 9 by a modified Polonovski reaction.
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■ Thermal [4π+2π]-Type Cycloaddition Reactions of Pyrrole Derivatives with 3-Cyanocyclopropene Generated in situ
Katsuhiro Saito,* Kazuaki Ito, and Kensuke Takahashi
*Faculty of Engineering, Nagoya Institute of Technology, Gokiso-cho, Showa-ku, Nagoya 466-8555, Japan
Abstract
Thermal reactions of 3-cyanocyclopropene with 1-methoxycarbonyl-, 1-benzoyl-, and 1-phenylpyrroles afforded [4π+2π]-type cycloaddition products, while 1-methyl- and 1-methyl-3-acetylpyrroles did not give any adducts. The adduct of 1-benzoylpyrrole existed as a mixture of two rotamers because of the hindered rotation of the carbamate group.
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■ Studies on Aconitum Species. XI. Two New Diterpenoid Alkaloids from Aconitum yesoense var. Macroyesoense (Nakai) Tamura V
Koji Wada, Hideo Bando,* Takashi Amiya, and Norio Kawahara
*Hokkaido College of Pharmacy, 7-1 Katsuraoka-cho, Otaru 047-02, Japan
Abstract
A new C20-diterpenoid alkaloid, yesonine (1), a new C19-diterpenoid alkaloid, α-oxobrowniine (2), and five known alkaloids were isolated from Aconitum yesoense var. macroyesoense (Nakai) Tamura. Structures of those new alkaloids were determined on the basis of their spectral and chemical correlation with known alkaloids. Hydrolysis of yesoline (9) and permanganate oxidation of browniine (10) afforded yesonine (1) and α-oxobrowniine (5), respectively.
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■ Cyclization Reactions of Arylhydrazone Adducts — Synthesis of 1-Aryl-1H-1,2,4-triazolo[4,3-b]indazoles
Giuseppe Cusmano, Gabriella Macaluso, Michelangelo Grueeadauria, and Silvestre Buscemi
*Dipartimento Chimica Organica, Università digli Studi di Palermo, Viale delle Scienze, 90128 Palermo, Italy
Abstract
The 1,3-addition reaction of nitrilimines to 3-indazolinone 11 and the acid assisted 6 π heteroelectrocyclic reaction of hydrazone adducts 13 have been investigated. Synthesis of the 1,3-substituted 1H-1,2,4-triazolo[4,3-b]-indazole system 17 via cyclization of 13 is described.
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■ Synthesis of (±)-Solenopsin A and (±)-Isosolenopsin A from 6-Methyl-2-piperidinone
Tatsuo Nagasaka,* Hideki Hayashi, Masaki Kumakawa, Masako Sakamoto, Masami Mizuno, and Fumiko Hamaguchi
*School of Pharmacy, Tokyo University of Pharmacy and Life Science, 1432-1 Horinouchi, Hachioji, Tokyo 192-0392, Japan
Abstract
(±)-Solenopsin A and (±)-isosolenopsin A were synthesized as a mixture in six steps from 6-methyl-2-piperidinone and they could be easily separated from each other as isomers.
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■ Studies in Cell Suspension Cultures of Cassia didymobotrya. Part II. The Biotransformation of Chalcones to Flavonones
B. Botta,* M. C. De Rosa, V. Vinciguerra, R. Scurria, P. Iacomacci, F. Ferrari, G. Delle Monache,* and D. Misiti
*Centro Chimica dei Recettori, C.N.R. , Università Cattolica del Sacro Cuore, Largo Francesco Vito 1, 00168 Roma, Italy
Abstract
An enzyme system derived from cell cultures of Cassia didymobotrya Showed, inter alia, a chalcone - flavanone isomerase which revealed a maximum activity when isolated from 22 day old cultures. Its substrate specificity was demonstrated by using sixteen chalcones featuring different substitutions patterns in rings A and B. The highest yields of flavanone formation were observed with various ring A functionalyzed chalcones lacking functionality in ring B. The chalcones having an isoprenyl side chain in the 3’- position of ring A were not transformed. The presence of a free hydroxyl group at C-4 of ring B stimulated flavanone formation relative to other ring B substrates. Some comments concerning the possible mechanism of the chalcone - flavanone isomerase reaction are provided.
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■ Studies in Cell Suspension Cultures of Cassia didymobotrya. Part III. The Biotransformation of Chalcones to Flavones and Biflavanones
B. Botta,* V. Vinciguerra, M. C. De Rosa, R. Scurria, A. Carbonetti, F. Ferrari, G. Delle Monache,* and D. Misiti
*Centro Chimica dei Recettori, C.N.R. , Università Cattolica del Sacro Cuore, Largo Francesco Vito 1, 00168 Roma, Italy
Abstract
Older (29 day) cell cultures of Cassia didymobotrya are shown to possess enzymes which can effectively catalyze the conversion of chalcones to flavone and novel biflavanone products. The substrates 2’,4,4’-trihydroxychalcone and 3-methoxy-2,4,4’-trihydroxychalcone were evaluated in terms of bioconversion yields versus time of incubation, and the effect, if any, of H2O2 and horseradish peroxidase on such bioconversions. Comments concerning the nature of the intermediates involved are presented.
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■ 13C Dynamic Nmr Studies on Restricted Rotation about C-N Bond in 2-Aryl-1-formyl-4-piperidones
Mario Rubiralta,* M. Pilar Marco, Miguel Feliz, and Ernest Giralt
*Laboratory of Organic Chemistry, Faculty of Pharmacy, University of Barcelona, Av. de Joan XXIII, s/n, 08028 Barcelona, Spain
Abstract
The synthesis of 1-formyl-2-(3-indolyl)-4-piperidone (7). trans-1-formyl-2-(3-indolyl)-3-methyl-4-piperidone (8), and their 4,4-ethyleneacetals 5 and 6 is described. The introduction of a formyl group on the piperidone nitrogen induces a change in the piperidine ring conformation such that the 2-indoiyl group is axial. However, in the 1-formyl-2-indolyl-4-piperidone 4,4-ethyleneacetals the indolyl group adopts an equatorial disposition due to a severe steric syn-diaxial interaction with the C-4 substituent. 13C-Dnmr is used to investigate the amide rotational barriers in a series of 2-aryl-1-formyl-4-piperidones.
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■ Facile Synthesis of Pyrrolo[2,3-d]pyrimidine and Pyrrolo[3,2-c]pyridine 2’,3’-Dideoxyribonucleosides via Nucleobase Anion Glycosylation with 2,3-Dideoxy-D-glycero-pentofuranosyl Chloride
F. Seela,* W. Bourgeois, H. -P. Muth, and H. Rosemeyer
*Laboratorium für Organische und Bioorganische, Institut für Chemie, Universität Osnabrück, Barbarastr. 7, D-4500 Osnabrück, Germany
Abstract
A facile synthesis of pyrrolo[2,3-d]pyrimidine and pyrrolo[3,2-c]pyridine 2’,3’-dideoxyribonucleosides employing a nucleobase anion and 2,3-dideoxy-D-glycero-pentofuranosyl chloride is described. The synthetic route allows large scale preparation of 2’,3’-dideoxytubercidin, 3,7-dideaza-2’,3’-dideoxyadenosine and related basemodified 2’,3’-dideoxyribonucleosides not accessible by conventional glycosylation techniques.
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■ A Novel Synthesis of 3-(2-Amino-4-ethoxyphenyl)pyridine
Kimiyuki Shibuya, Yoshio Takahashi, Hiromichi Shigyo, and Tomio Ohta*
*Tokyo Research Laboratories, Kowa Co., Ltd., 2-17-43, Noguchi-cho, Higashimurayama 189, Japan
Abstract
A novel and efficient synthesis of 3-(2-amino-4-ethoxyphenyl)pyridine (2), a key intermediate of the antiarrhythmic agents, has been developed starting from p-cresol (3).
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■ Synthetic Approach toward Azinomycins
Kenshi Ando, Takae Yamada, and Masayuki Shibuya*
*Faculty of Pharmaceutical Sciences, University of Tokushima, Sho-machi 1, Tokushima 770-8505, Japan
Abstract
The left-half segment 14 of antitumor antibiotics azinomycins A and B was synthesized in optically pure form staning from D-fructose. The dipeptide 18, equivalent to the azinomycin A top-half, was also synthesized via oxazolidinone intermediates.
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■ Catalytic Asymmetric Synthesis of 2- and 3-Furylcarbinols
Kenso Soai,* Yasuhiro Kawase, and Seiji Niwa
*Department of Applied Chemistry, Faculty of Science, Science University of Tokyo, Kagurazaka 1-3, Shinjuku-ku, Tokyo 162-8601, Japan
Abstract
Optically active 2- and 3-furylcarbinols were synthesized in high enantiomeric excesses (up to 94% e. e.) by the enantioselective addition of dialkylzinc reagents to 2- or 3-furaldehydes using N,N-dibutylnorephedrine and (S)-diphenyl(1-methylpyrrolidin-2-yl)methanol as chiral catalysts.
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■ Literature Review of the Ester Enolate Imine Condensation
Mark J. Brown*
*Department of Chemistry, University of California, Irvine, Irvine, California 92697, U.S.A.
Abstract
A review of the ester enolate imine condensation to give β-lactams and or β-amino esters is presented.