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. 36, No. 7, 1993
Published online:
■ Lamarckinine, a New Bisnorditerpenoid Alkaloid from Aconitum lamarckii Reichenb.
Gabriel de la Fuente,* Tomás Orribo, José A. Gavín, and Rafael D. Acosta
*Instituto de Productos Naturales y Agrobiologia de Canrias, CPNO "Antonio Gonz!aez", C. S. I. C./ Unversidad de La Laguna, P.O. Box 195, 38206- La Laguna, Tenerife, Spain
Abstract
A new bisnorditerpenoid alkaloid lamarckinine (1) containing a C(19) = N- azomethine group was isolated from Aconitum lamarckii Reichenb., besides neoline, 1,14-diacetylneoline, 8-O-ethylbenzoylaconine, columbianine, delcosine, lycoctonine, and 18-methoxygadesine. The structure of the new alkaloid was elucidated by 2D nmr spectroscopy and its conversion into deoxymethylenelycoctonine.
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■ Novel Condensation Reactions of N-Cycloheptatrienylidene Alkylamine N-Oxides with Acetylene Derivatives: Facile Formation of 1-Azaazulen-2(1H)-ones
Kazuaki Ito, Katsuhiro Saito,* and Kensuke Takahashi
*Department of Applied Chemistry, Nagoya Institute of Technology, Gokiso-cho, Showa-ku, Nagoya 466-8555, Japan
Abstract
Reactions of N-cycloheptatrienylidene alkylamine N-oxide with acetylene derivatives having electron attracting group afforded 1-azaazulen-2(1H)-one derivatives through a unique condensation process leaving methyl formate or hydrogen.
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■ Pd(0)-Catalysed Synthesis of Buspirone and Gepirone
David L. Kuo
*Research and Development Department, Lonza Ltd., Walliser Werke, CH-3930 Visp, Switzerland
Abstract
A novel synthetic approach to buspirone and its anologue (gepirone) is described, in which 3 subunits, namely 2-(1-piperazinyl)pyrimidine, a bifunctional allylderivative, and an imide were efficiently assembled via a Pd(0)-catalysed amination-imidation sequence followed by a hydrogenation.
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■ Synthesis of Some 5,6-Dihydro-7H-1,4,2-oxathiazepin-7-ones and 5H-4,1,3-Benzoxathiazepin-5-ones
Wynona Johnson, Stuart Littler, and Colin Skene*
*CSIRO, Division of Chemicals and Polymers, Praivate Bag 10, Clayton, South MDC, Victoria, 3168, Australia
Abstract
The novel heterocyclic systems 5,6-dihydro-7H-1,4,2-oxathiazepin-7-one (1) and 5H-4,1,3-benzoxathiazepin-5-one (2) were prepared by the reaction of hydroximoyl chlorides (3) with mercapto-carboxylic acids, followed by cyclization with 1,3-dicyclohexylcarbodiimide (6) or 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide HCl (7).
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■ Photochemical Reaction of 6-Alkoxy-7-(2-oxoalkyl)quinoline-5,8-quinones
Katsuhiko Nakagawa,* Hirofumi Kaneko, Takashi Yano, Shigehiro Inai, Kenzo Tabuchi, and Shozo Shimada
*Department of Industrial Chemistry, Niihama National College of Technology,7-1 Yagumo-machi, Niihama, Ehimie 792, Japan
Abstract
Photochemical reaction of 6-alkoxy-7-(2-oxoalkyl)quinoline-5,8-quinones in benzene gave a novel heterocyclic quinones, 2-aklyl-4-methylquino[6,7-d][1,3]dioxepine-6,11-diones via intramolecular γ-H-abstraction.
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■ A Regiospecific Synthesis of Carbazoles via Consecutive Palladium-catalyzed Cross-Coupling and Aryne-mediated Cyclization
Masatomo Iwao,* Hirokazu Takehara, Sunao Furukawa, and Mitsuaki Watanabe*
*Faculty of Liberal Arts, Nagasaki University, 1-14, Bunkyo-machi, Nagasaki 852-8521, Japan
Abstract
A regiospecific synthesis of carbazoles has been developed using palladium-catalyzed cross-coupling of N-(tert-butoxycarbonyl)-2-tributylstannylanilines with 2- or 3-bromochlorobenzene followed by aryne-mediated cyclization as the key reactions. The carbazole alkaloids, glycozolinine and glycozolidine, were synthesized using this procedure.
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■ Synthesis of (-)-Nonactic Acid: Application of γ-Dithio-β-hydroxy Ester Prepared by Microbial Reduction as a Chiral Building Block
Kazuhiko Takatori, Nobuyuki Tanaka, Kenji Tanaka, and Masahiro Kajiwara*
*Department of Medicinal Chemistry, Meiji College of Pharmacy, 1-22-1 Yato-cho, Tanashi-shi, Tokyo 188, Japan
Abstract
A γ-dithio-β-hydroxy ester (2), prepared by microbial reduction with baker’s yeast, was used as a chiral building block, for the synthesis of (-)-nonactic acid (1). It was converted to the lithium acetylide via 5, of which 1,2-addition to the aldehyde (6) followed by reduction gave the 3-silyloxy-6-tosyloxynonane (8b). On cleavage of the silyl ether, cyclization proceeded with complete inversion of configuration at C-6 to afford a cis-2,5-disubstituted tetrahydrofuran (9), which was led to 1.
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■ A New Potential Acyl Iminium Ion for the Asymmetric Synthesis of Piperidine Derivatives
Jacques Royer and Henri-Philippe Husson*
*Institut des Chimie des Substances Naturelles, C.N.R.S., 1 avenue de la Terrasse, Bat. 27, 91198 Gif-sur-Yvette Cedex, France
Abstract
Epimeric oxazolopiperidones (1a) and (1b) were prepared independently, both from R-(-)-phenylglycinol as starting material. They represent chiral potential iminium ions.
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■ Reaction of 2-Trimethylsilylmethylthiopyridine Promoted by a Fluoride Ion: The First Example of Generation of 2-Pyridylthiomethylcarbanion
Shinya Kohra,* Hiroshi Ueda, and Yoshinori Tominaga
*Faculty of Liberal Arts, Nagasaki University, 1-14, Bunkyo-machi, Nagasaki 852-8521, Japan
Abstract
2-Trimethylsilylmethylthiopyridine prepared readily by the reaction of 2-mercaptopyridine with chloromethyltrimethylsilane in the presence of potassium carbonate reacts with carbonyl compounds in the presence of a catalytic amount of tetrabutylammonium fluoride (TBAF) to give 2-(2-pyridylthio)ethanols. This reaction is the first example of generation and introduction of 2-pyridylthiomethylcarbanion.
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■ Two New Coumaronochromone Derivatives, Oblongin and Oblonginol from the Roots of Derris oblonga Benth
Yun-Lian Lin and Yueh-Hsiung Kuo*
*Department of Chemistry, National Taiwan University, Roosevelt Road Section 4, Taipei 106, Taiwan, R.O.C.
Abstract
Two new coumaronochromone derivatives, oblongin and oblonginol, have been isolated from the roots of Derris oblonga. Their structures have been elucidated by spectroscopic and chemical methods.
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■ Synthesis of N-Demethyl-N-substituted 14β-Hydroxy isomorphine and Dihydroisomorphine Derivatives
Sándor Hosztafi, Csaba Simon, and Sándor Makleit*
*Department of Organic Chemistry, Lajos Kossuth University, P.O.Box 20, H-4010 Debrecen, Hungary
Abstract
Some new representatives (3e-3h, 5g) of a new group of structurally related morphine-agonist and antagonist compounds have been prepared in stereochemically homogeneous forms. Application of the Mitsunobu-reaction for suitable codeine derivatives (1a-1d) gave the benzoates (2a-2d) of the hitherto unknown C-6 iso-compounds, which were converted into the desired isocodeines (3b-3d) by means of alkaline hydrolysis. O-Demethylation of these derivatives afforded the corresponding morphine analogues. The preparation of 3e was also carried out from 1f via compound (2e). A hitherto unknown N-demethylation also allowed the conversion of 3a and 5a into the target compounds. With the exception of N-allyl derivatives, the dihydro analogues were obtained by the hydrogenation of the C7-C8 double bond.
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■ A Simple Method for Synthesis of 4-Dimethylamino-2,6-dimethyl-5-phenylpyrimidines
Wojciech Zielinski* and Monika Mazik
*Instiute of Organic Chemistry and Technology, Silesian University of Technology, ul. Krzywoustego 4, 44-101 Gliwice, Poland
Abstract
The reaction of N-(1-methyl-2-phenylvinyl)acetimidoyl chloride and its derivatives substituted at the benzene ring with N,N-dimethylcyanamide was studied. At the first stage, linear products like 1-chloro-1-dimethylamino-3,5-dimethyl-6-phenyl-2,4-diaza-1,3,5-hexatrienes were obtained. They underwent cyclization to 4-dimethylamino-2,6-dimethyl-5-phenylpyrimidines in alkaline medium at elevated temperature.
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■ Synthesis of Penams from 1H-Azetidinones by Intramolecular Carbenoid Insertion
Pierluigi Bissolino, Marco Alpegiani, Daniela Borghi, Ettore Perrone, and Giovanni Franceschi*
*Farmitalia Carlo Erba R&D, Via C.Imbonati 29, 20146 Milano, Italy
Abstract
Construction of the penam ring system has been achieved by dirhodium tetraacetate cyclization of 4-thio-1H-azetidinone derivatives bearing an α-diazoester appendage. The sulfur atom of 4-thioethers interferes by reacting with the electrophilic metal carbene, but the corresponding sulfone and sulfoxides undergo the prescribed cyclization exclusively. Nmr studies on obtained bisnorpenams indicate pseudoequatorial puckering for the thiazolidine ring of the S-sulfoxide, while the parent sulfide and the R-sulfoxide exist as pseudoaxial conformers.
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■ SRN1 Reactions in Imidazo[1,2-a][1,8]naphthyridine Series
Patrice Vanelle,* Saïd Ghezali, José Maldonado, Olivier Chavignon, Alain Gueiffier, Jean-Claude Teulade, and Michel P. Crozet*
*Radicaux Libres et Synthèse, CNRS URA 1412, Université e’Aix-Marseille III, Faculté des Sciences et Techniques de St.-Jérôme, Avenue Escardrille Normandie-Niemen BP 562,13397 Marseille Cedex 20, France
Abstract
8-Chloromethyl-2,4-dimethyl-9-nitroimidazo[1,2-a][1,8]naphthyridine was synthesized as reductive alkylating agent and its reactivity with 2-nitropropane anion was investigated. The SRN1 mechanism of the C-alkylation was confirmed by the inhibitory effects of p-dinitrobenzene, molecular oxygen and TEMPO. Extension of this SRN1 reaction to various nitronate anions leads after nitrous acid elimination to a new class of imidazo[1,2-a][1,8]naphthyridine derivatives bearing a trisubstituted double bond at the 8 position.
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■ Studies on Quinones. Part 26. The Reaction of Methacrolein N,N-Dimethylhydrazone with Activated Benzoquinones
Jaime A. Valderrama* and M. Florencia González
*Facultad de Química, Pontificia Universidad Católica de Chile, Casilla 306, Correo 22, Santiago, Chile
Abstract
A one-step formation of 5-hydroxy-2,3-dihydrobenzo[b]furans by a [3+2] addition process of methacrolein N,N-dimethylhydrazone (4) with a variety of 1,4-benzoquinones bearing activating groups is reported.
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■ The Chemistry of Polyphyrins 2. Syntheses of Hexaphyrins and Their Metal Complexes
Roland Charriere, Titus A. Jenny, Hans Rexhausen, and Albert Gossauer*
*Institut für Organische Chemie, Universität Freiburg I. Ue., ret. du Musée, CH-1700 Fribourg, Switzerland
Abstract
The synthesis of eight derivatives of a 26 π-electron macrocycle analogous to the porphyrins bearing six pyrrole rings and six methine bridges is described. This chromophore is named hexaphyrin. Owing to the flexibility of their chromophore, hexaphyrins are able to form two kind of binuclear coordination complexes of substantially different geometry.
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■ Rearrangement of 3-(N-Heteroarylamino)-1,2,5-oxadiazoles: Triazolo[1,5-a]quinolines and Triazolo[1,5-a]pyridines
Giuseppe Cusmano,*Gabriella Macaluso, and Michelangelo Gruttadauria
*Dipartimento di Chimica Organica, Università digli Studi di Palermo, Via Archirafi 20 90123 Palermo, Italy
Abstract
The rearrangement reaction of 1,2,5-oxadiazole derivatives bearing quinoline and pyridine heterocycles in a N-C-N side chain sequence was investigated. Triazolo[1,5-a]quinoline and triazolo[1,5-a]pyridine oximes were obtained in good yield.
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■ A New Synthetic Route to the Previously Unattainable 3-Substituted 2,3-Dihydro-1,4-dioxino[2,3-b]pyridines
Abdelhakim Benarab, Pascal Poirot, and Gerald Guillaumet*
*Laboratoire de Chimie Bioorganique et Analytique, URA-CNRS N° 499, Université d’Orléans, BP 6759, Rue de Chartres, 45067 Orleans Cedex 2, France
Abstract
A variety of 3-substituted-2,3-dihydro-1,4-dioxino[2,3-b]pyridines (3) have been synthesized from the readily available 2-chloro-3-oxiranylmethoxypyridine (1). Treatment of this epoxide by various nucleophile reagents provided alcohols (2a-i) which, by displacement of the chlorine, gave the desired products (3a-i) in satisfactory yields.
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■ Synthesis of Thioaldehydes Having Optically Active Alkoxy Moiety and Their Asymmetric Hetero Diels-Alder Reaction
Tamiko Takahashi, Noriyuki Kurose, Toru Koizumi,* and Motoo Shiro*
*Faculty of Pharmaceutical Sciences, Toyama Medical and Pharmaceutical University, 2630 Sugitani, Toyama, Toyama 930-0194, Japan
Abstract
Optically active α-alkoxycarbonylthioaldehydes (2a-g) were prepared using 8-arylmethols as chiral auxiliaries. Their asymmetric hetero Diels-Alder reactions with cyclopentadiene gave the endo cycloadducts (3 and 4) and exo cycloadducts (5 and 6) with moderate diastereomeric excesses. However, the major endo cycloadducts (3b-g) were isolated in optically pure form. This is the first chiral synthesis of 2-thiabicyclo[2.2.1]hept-5-ene ring system. The absolute configuration of the cyclic carbonate (12), which was prepared from the major endo cycloadduct (3c) via the epimerization, or the minor exo compound (6c), was determined as 1R by X-ray analysis. The cycloadduct (3c) was transformed to a potential intermediate (14) for the synthesis of carbocyclic homonucleosides.
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■ C-Nucleosides. 21. Synthesis of Isoxazole C-Nucleoside from Furanone Glycoside via Enaminone Glycoside
Isamu Maeba,* Yasutaka Ito, Masakazu Wakimura, and Chihiro Ito
*Faculty of Pharmacy, Meijo University, 150 Yagotoyama, Tenpaku, Nagoya 468-8503, Japan
Abstract
Synthesis of the versatile and stable C-nucleoside precursor enaminone glycosides (3a,b) was achieved by reaction of furanone glycoside (1) with 2- and 4-aminophenols. Treatment of enaminone (3b) with hydroxylamine hydrochloride yielded 5-hydroxy-4,5-dihydroisoxazole (5), which on dehydration with toluene-p-sulfonic acid in benzene gave 5-(2,3,5-tri-O-benzoyl-β-D-ribofuranosyl)isoxazole (6). Deblocking of compound (6) with sodium carbonate gave 5-(β-D-ribofuranosyl)isoxazole (7).
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■ The Alkylation of 2-Amino-6-chloropurine with Alcohols by Mitsunobu Reaction for a Synthesis of Carbocyclic Guanosine Analogs
Akemi Toyota,* Nobuya Katagiri, and Chikara Kaneko
*Phamaceutical Institute, Tohoku University, Aramaki, Aoba-ku, sendai 980-8578, Japan
Abstract
Mitsunobu reaction of 2-amino-6-chloropurine with various alcohols which provides a convenient method for a synthesis of carbocyclic or acyclic guanosine analogs is described.
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■ Synthesis of Novel, Fused Benzoxazocines by an Unexpected Intramolecular Cyclisation
William J. Coates and Dashyant Dhanak*
*SmithKline Beecham Pharmacuticals, The Frythe, Welwyn, Hertfordshire, AL6 9AR, U.K.
Abstract
Novel, fused benzoxazocines are obtained from the treatment of 2-(2-(3-hydroxypropoxy)phenyl)benzimidazole and imidazopyridine derivatives with trifluoroacetic anhydride followed by heating in HMPA.
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■ A One-Step Synthesis of 2,3-Diydro-1,4-benzothiazines and Phenothiazines from 1,3-Thiazolidine Derivatives of Cyclohexanones
Romualdo Caputo, Carla Ferreri,* Luigi Longobardo, Domenico Mastroianni, Giovanni Palumbo,* and Silvana Pedatella
*Dipartimento di Chimica Organica e Biologica, Università di Napoli "Federico II", Via Mezzocannone 16, I-80134 Napoli, Italy
Abstract
N-Acetyl-1,3-thiazolidine derivatives of cyclohexanones, when treated with a threefold excess N-bromosuccinimide in anhydrous chloroform at room temperature, smoothly afford N-acetyl-2,3-dihydro-1,4-benzothiazines. This represents the first general route to such heterocyclic system in one step from aliphatic precursors. The synthesis of optically active N-acetyl-2,3-dihydro-1,4-benzothiazines is also reported.
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■ Host-Guest Complexes of Azaaromatic Quaternary Salts
Wanda Sliwa,* Lidia Chrzastek, and Marian Mielniczak
*Institute of Chemistry, Pedagogical University, 25-020 Kielce, Poland
Abstract
Inclusion complexes, where azaaromatic quaternary salts serve as a guest or as a host are described, along with related rotaxanes and catenanes.