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. 2, 1989
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■ Diterpenoid Alkaloids from Delphinium pictum Willd. The Structure of Pictumine
Gabriel de la Fuente,* Rafael Díaz Acosta, and Tomás Orribo
*Centro de Productos Naturales Orgánicos "Antonio González", Universidad de La Laguna, Avda. Astrofísico Franciso Sánchez, 2, 38206- La Laguna, Tenerife, Spain
Abstract
A new C-19 diterpenoid alkaloid pictumine (1) was isolated from Delphinium pictum Willd. subsp. pictum together with the known bases neoline (2), bullatine C (14-acetylneoline) (3), delphisine (8,14-diacetylneoline) (4), delphinine (5), chasmaconitine (6), and chasmanthinine (7). The structure of the new alkaloid was established by 1H and 13C-nmr spectra. The 13C-nmr data for alkaloids (3), (6), and (7) are also presented.
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■ Cleavage Reactions of Penicillin Nuclei with Seyferth Reagents
Jahyo Kang,* Weon Bin Im, Soon-gyu Choi, Daesung Lim, Young Ro Choi, Hyung Geun Cho, and Jae Hyoung Lee
*Department of Chemistry, Sogang University, Mapoku, Seoul 121-742, Korea
Abstract
Various penams were converted to the corresponding 4-dihalomethylthio-azetidinones by PhHgCX3.
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■ An Efficient Cyclosulfurization of N-(2-Hydroxyphenyl)thioamides with Superoxide. A Novel Route to Benzoxazoles
Yong Hae Kim,* Yong Il Kim, Hae Subg Chang, and Dae Chul Yoon
*Department of Chemistry, Korea Advanced Institute of Science and Technology, 373-1, Kusung-Dong, Yusung-Gu, Taejon, 305-701, Korea
Abstract
Treatment of N-(2-hydroxyphenyl)thioamides (1) with superoxide (02-/) at room temperature in dry acetonitrile resulted in the formation of 2-substituted benzoxazoles (7) in excellent yields.
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■ The Reduction of 4-Acyk-β-lactams with Sodium Borohydride. A Possible Dichotomy of Stereochemical Pathways
Benito Alcaide, Gema Dominguez, and Joaquín Plumet*
*Departamento de Química Orgánica, Facultad de Ciencias, Universidad de Extremadura, Avenida de Elvas s/n, 06071-Badajoz, Spain
Abstract
Stereochemical result of the sodium borohydride reduction of 4-acyl-β-lactams to 4(α-hydroxyalkyl)-β-lactams is reported. The stereoselectivity is accounted for by competition between two possible stereochemical pathways,
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■ The Absolute Configuration of (+)-Canadaline
Miyoji Hanaoka,* Kazuyoshi Nagami, and Shingo Yasuda
*Faculty of Pharmaceutical Scicences, Kanazawa University, 13-1 Takara-machi, Kanazawa 920-0934, Japan
Abstract
The absolute configuration of natural (+)-canadaline (1) was established to be S-configuration by its biomimetic synthesis from S-(-)-canadine (5).
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■ Falconericine and Falconeridine: Two New Alkaloids from Aconitum falconeri Stapf.
Haridutt K. Desai and S. William Pelletier*
*Department of Chemistry, Institute for Natural Products Research, The University of Georgia, Chemistry Building, Athens, Georgia 30602-2556, U.S.A.
Abstract
Two new C19-diterpenoid alkaloids, falconericine (1) and falconeridine (2) have been isolated from the roots of Aconitom falconeri Stapf. and their structures deduced by spectroscopic methods and chemical correlation with alkaloids of established structures. A third alkaloid, falconeridinine (3) is likely an artefact of the isolation conditions. It has been synthesized by refluxing a solution of falconerine-8-acetate in ethanol.
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■ Praziquantel Analogues. II. Synthesis of 4-Oxo-octahydropyrazino[1’,2’:1,2]pyrido[3,4-b]- and -[4,3-b]indoles
Nativitat Valls, Víctor M. Segarra, Xavier López, and Joan Bosch
*Laboratory of Organic Chemistry, Faculty of Pharmacy, University of Barcelona, Av. de Joan XXIII, s/n, 08028 Barcelona, Spain
Abstract
The title compounds 1a and 3 have been synthesized by cydization of the N-acyliminium ion generated from 1-(3-indolylethyl)piperazinedione 7 and by Pictet-Spengler condensation between isotryptamine and ester acetal 2a, respectively.
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■ Addition of Indoles to N-Alkylpyridinium Salts. Synthesis of (Dihydropyridyl)indoles
Mercedes Alvarez, Rodolfo Lavilla, and Joan Bosch*
*Laboratory of Organic Chemistry, Faculty of Pharmacy, University of Barcelona, Av. de Joan XXIII, s/n, 08028 Barcelona, Spain
Abstract
The addition of the sodium salt of several indole derivatives 1 to N-alkylpyridinium salts 2 having an electron-withdrawing substituent at the β-position is studied.
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■ A New Enantioselective Route to (+)-Quebrachamine
Morio Asaoka* and Hisashi Takei
*Department, Graduate School of Bioscience and Biotechnology, Tokyo Institute of Technology, 4259 Nagatsuta-cho, Midori-ku, Yokohama 226-8501, Japan
Abstract
Formal synthesis of (+)-quebrachamine was achieved using a new chiral building block 3-ethyl-5-trimethylsilyl-2-cyclohexenone.
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■ Ring Transformation of 1,2,6-Thiadiazine 1,1-Dioxides into Pyrazoles. A Convenient Syntjesis of N-Alkylsulfamides
José Elguero, Pilar Goya, and Ana Martínez
*Instituto de Química Orgánica General, C. S. I. C., Calle Juan de Cierva, 3, 28006 Madrid, Spain
Abstract
Conversion of thiadiazines into pyrazoles by the action of hydrazine represents a new example of ring transformation and provides a new entry into N-methylsulfamide. The latter has been used to prepare an N-methyl-3,5-diaminothiadiazine which cannot be obtained by direct alkylatian.
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■ Nucleophilic Cleavage of (2S,3S)-3-Phenylglycidol
Seiichi Takano,* Masashi Yanase, and Kunio Ogasawara
*Pharmaceutical Institute, Tohoku University, Aramaki, Aoba-ku, Sendai 980-8578, Japan
Abstract
Reaction of (2S,3S)-3-phenylglycidol with a variety of nucleophiles has been examined. The reaction occurred regioselectively at the benzylic center generally with an excellent diastereoselectivity. Although most of the nucleophiles yielded the products with inversion of the original chirality, trimethylaluminum furnished the retention product in a high diastereoselectlvity.
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■ The Nucleophilic Reaction of Tricarbonyl(2-3-η-1H-azepine)iron. Novel Prepration and Thermal 1,5-Hydrogen Migration of 3-(1,3,5-Cycloheptatrien)-3H-azepine
Makoto Nitta,* Kazusato Shibata, and Hiroyuki Miyano
*Department of Chemistry, School of Science and Engineering, Waseda University, 3-4-1 Okubo, Shinjuku-ku, Tokyo 169-8555, Japan
Abstract
The nucleophilic reaction of tricarbonyl (2-5-η-1H-azepine) iron with tropylium cation and several electrophiles was studied. The decomplexation giving 3-(2,4,6-cycloheptatrienyl)-3H-azepine and its novel 1,5-hydrogen migration in the azepine ring are discussed.
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■ The Di-π-methane Rearrangement in 3,4-Dibenzyl-2(5H)-furanone
Takefumi Momose,* Genzoh Tanabe, Hisayuki Tsujimori, Mié Higashiura, Ichiroh Imanishi, and Kenichi Kanai
*Faculty of Pharmaceutical Sciences, Kinki University, 3-4-1, Kowakae, Higashi-Osaka 577-8502, Japan
Abstract
The photo-irradiation of 3,4-dibenzyl-2(5H)-furanone (5) in acetone or in methanol resulted in selective rearrangement of the 4-benzyl and gave 1-benzyl-5-phenyl-3-oxabicyclo[3.1.0]hexan-2-one (7) along with cis- and trans-3,4-dibenzyldihydro-2 (3H)-furanone (8a and 8b). Attempted rearrangement of the 3-benzyl system (13) resulted only in photo-reduction or photo-addition of solvent and gave no evidences for the di-π-methane rearrangement.
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■ Reinvestigation of Cycloaddition of Nitrosobenzene towards 1,3-Diphenylisobenzofurans
Cheng-Tung Lin,* Li-Wei Din, and Sue-Lein Wang
*Department of Chemistry, Tunghai University, Taichung, Taiwan 40098, Taiwan, R.O.C.
Abstract
The title reaction gives rearrangement product of N-phenyl-α-phenyl-α-(o-benzoylphenyl)nitrones (8) rather than the earlier reported Diels-Alder cycloadduct 2. The molecular structure of 8a has been confirmed by a single crystal X-ray diffraction study.
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■ Synthesis of Natural (S)-(—)-Tulipalin B Starting from L-Malic Acid as a Chiral Pool
Osamu Muraoka, Naoki Toyooka, Yumiko Ohshima, Norihiko Narita, and Takefumi Momose*
*Faculty of Pharmaceutical Sciences, Kinki University, 3-4-1, Kowakae, Higashi-Osaka 577-8502, Japan
Abstract
The naturally occurring α-methylene-γ-lactone Tulipalin B (2) was synthesized enantioselectively starting from L-malic acid as a chiral pool in 15% overall yield.
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■ Base-catalysed Condensation of 2,5-Dimethy-1-phenylpyrrole-3,4-dicarbaldehyde with β-Diketones
Jasna Vorkapic-Furac* and Mihela Suprina
*Faculty of Food Technology and Biotecnology, University of Zagreb, 41000 Zagreb, Croatia
Abstract
The base-catalysed condensation of 2,5-dimethyl-1-phenylpyrrole-3,4-dicarbaldehyde with 2,4-pentanedione and 1-(p-methoxyphenyl)-1,3-butanedion has been investigated under different reaction conditions (e.g. solvent, catalyst, temperature, time).
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■ Synthesis of Some β-(1-Benzimidazolyl)- and β-(1-Benzotriazolyl)-α-amino Acid Derivatives
Mojca Dobnikar, Marijan Kocevar, Slovenco Polanc, Miha Tisler, and Bojan Vercek*
*Department of Chemistry and Chemical Technology, E. Kardelj University, Murnikova 6, 61000 Ljubljana, Slovenia
Abstract
A convenient method for the preparation of methyl β-(1-benzimidazolyl)- and β-(1-benzotriazolyl)-α-benzoylaminoacrylates (5) from N-substituted o-phenylenediamine 2a is described. The synthesis of these two compounds proceeds either by ring opening of oxazolones 3 or by cyclization of acrylates 4.
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■ [4+2]Cycloadducts of 5-Benzyloxy-2-pyridone with Electron Deficient Dienophiles. Regio- and Stereochemistry
Claus Herdeis* and Claudia Hartke
*Institut für Pharmazie und Lebensmittelchemie, Universität Wurzburg, Am Hubland, D-97074 Wurzburg, Germany
Abstract
The electron-rich 2-pyridone 4 is converted into the 2-azabicyclo [2.2.2] octane derivatives 8-12 via [4+2] cycloaddition. 10b is transformed to vinyl sulfone 6, an intermediate in a potential route to ibogamine 1. The regio- and stereochemistry of the cycloaddition reaction is reported.
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■ Sigmatropic Rearrangement in Synthesis of C-8 Prenylated 3-(1’,1’-Dimethylallyl)coumarins: 3-(1’,1’-Dimethylallyl)seselin
Rosario Hernández Galán, Guillermo M. Massanet, Enrique Pando, Francisco Rodríguez Luis, and Javier Salvá
*Departamento de Química Orgánica, Facultad de Ciencias, Universidad de Cádiz, Apartado 40, Puerto Real (Cádiz), Spain
Abstract
Synthesis of angular pyranocoumarin 3-(1’,1’-dimethylallyl)seselin, via sigmatropic rearrangement and prenylation of the romatic ring in good overall yiled is described.
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■ 17O Nmr Spectroscopy of Lactones
David W. Boykin,* David W. Sullins, and E. J. Eisenbraun
*Department of Chemistry, Georgia State University, University Plaza, Atlanta, GA 30303, U.S.A.
Abstract
Natural abundance 17O nmr spectroscopic data for 30 lactones acquired in acetonitrile at 75°C are reported: relationships beween 17O chemical shift and structure are discussed.
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■ 17O Nmr Spectroscopy of Lactams
David W. Boykin,* David W. Sullins, N. Pourahmady, and E. J. Eisenbraun
*Department of Chemistry, Georgia State University, University Plaza, Atlanta, GA 30303, U.S.A.
Abstract
Natural abundance 17O nmr spectroscopic data for 36 lactams acquired in acetonitrile at 75°C are reported: relationships between 17O chemical shift and structure are discussed.
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■ Heterocyclic Spiro Compounds. III. Synthesis of [2R*,11bR*]-9.10-Dimethoxy-1,3,4,6,7,11b-hexahydrobenzo[a]quinolizine-2-spiro-3’-pyrrolidines and [2R*,11bR*]-9,10-Dimethoxy-1,3,4,6,7,11b-hexahydrobenzo[a]quinolizine-2-spiro-3’-pyrrolidin-2’-ones
J. Carlos Menéndez and Mónica M. Söllhuber*
*Departamento de Química Orgánica y Farmacéutica, Facultad de Farmacia, Universidad Complutense de Madrid, Ciudad Universitaria, 28040 Madrid, Spain
Abstract
The stereochemistry of succinimides 1, pyrrolidines 2 and pyrrolidinones 3 is reported on the basis of spectroscopic data. The results of the reduction of 1 with lithium aluminum hydride and diborane are described.
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■ Ab Initio Quantum-Chemical Study of the Influence of Mehtyl Substitution on the Redox Behaviour of 1,4-Dihydronicotinamides. Part 2: The Supermolecule Approach.
Jan D. Bossaerts, Frank C. Alderweireldt, and Paul Geerlings*
*Eenheid Algemene Chemie (ALGC), Fakulteit Wetenschappen, Vrije, Universiteit Brussel, Pleinlaan 2, B-1050 Brussel, Belgium
Abstract
Ab initio minimal basis set quantum-chemical calculation on the interaction between methylated N-alkyl-1,4-dihydronicotinamides and the simplest keto derivative (formaldehyde) are reported. The supermolecule approach provides a distinctive improvement in the interpretation of the experimentally determined reactivity of the dihydronicotinamides in their reaction with keto compounds, as compared to previously used models (e.g. Krechl’s elongation model1,2) .
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■ Rearrangements of Arylhydrazones of N-Acylbenzimidazoles - Synthesis of 2-Aryl-1,2,4-triazolo[4,3-a]quinoxalinium Salts
Giuseppe Cusmano and Gabriella Macaluso
*Dipartimento Chimica Organica, Università digli Studi di Palermo, Viale delle Scienze, 90128 Palermo, Italy
Abstract
The acid induced rearrangement of arylhydrazones of N-acylbenzimidazoles has been investigated. An initial 6π heteroelectrocyclic reaction involving the hydrazone side chain and the imidazole moiety, followed by a ring opening gave 4-(2-aminopheny1)-1,2,4-triazolium perchlorate 7 as intermediates. The latter species, depending on the substituent present in the triazole moiety, gave the 2-aryl-1,2,4-triazolo[4,3-a]quinoxalinium perchlorates 8 or 9 as the final rearranged products. Alkaline cleavage of the triazolo[4,3-a]quinoxalinium perchlorates 8 and 9 to 3-(arylformylhydrazino)guinoxaline derivatives 11 and 13 has been pointed out.
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■ Reactivity of Isoselenazoles towards Nucleophilic Reagents
Francesco Lucchesini, Nevio Picci, Marco Pocci, Angela De Munno,* and Vincenzo Bertini
*Dipartimento di Chimica e Chimica Industriale, Università di Pisa, Via Risorgnimento 35, I-56126 Pisa, Italy
Abstract
Isoselenazoles have shown two reactive sites towards nucleophiles. LDA gives metallation in the 5-position exploited for synthetic purposes. Grignard reagents and LAH attack the selenium atom forming non-cyclic functionalized systems.
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■ A New Neoflavanoid from Coutarea hexandra
Giuliano Delle Monache,* Bruno Botta, Vittorio Vinciguerra, and Eszter Gacs-Baitz
*Centro Chimica dei Recettori, C.N.R. , Università Cattolica del Sacro Cuore, Largo Francesco Vito 1, 00168 Roma, Italy
Abstract
A new neoflavone was isolated from Coutarea hexandra and assigned to 7,3’,4’-trihydroxy-5-methoxy-4-phenylcoumarin.
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■ New Atypical Antidepressants: An Efficient Process for Preparing cis-1,3,4,6,7,11b-Hexahydro-2-methyl-7-aryl-2H-pyrazino[2,1-a]isoquinolines
Richard J. Schmiesing* and James R. Matz
*Department of Organic Chemistry, Pharmaceutical Division, Pennwalt Corporation, Rochester, New York 14623, U.S.A.
Abstract
Starting from 3-phenyl-2,piperazinone,cis-1,3,4,6,7,11b-hexahydro-2-methyl-7(4-chlorophenyl)2H-pyrazino[2,1-a] isoquinoline (1) was synthesized utilizing as the pivotal step of the sequence a highly stereocontrolled base-catalyzed equilbration bration of 3,4,6,7-tetrahydro-7(4-chlorophenyl)-2H-pyrazino[2,1-a]isoquinolin-1(11bH)-ones (2).
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■ Mild Synthesis of N-Alkyl- and N-Alkyl-β-carboline Anhydoro-bases Using Trifluoromethanesulfonates
Robert H. Dodd,* Guillaume Poissonnet, and Pierre Potier
*Institut des Chimie des Substances Naturelles, C.N.R.S., 1 avenue de la Terrasse, Bat. 27, 91198 Gif-sur-Yvette Cedex, France
Abstract
Hindered 3-substituted pyrido[3,4-b]indoles (1-3) were quaternized in good yield using various alkyl trifluoromethanesulfonates generated in situ from the corresponding alcohol and trifluoromethanesulfonic anhydride in the presence of diisopropylethylamine in CH2Cl2. The resulting salts (4-13) were allowed to react with Cs2CO3 in refluxing DME to give the corresponding β-carboline anhydrobases (14-23). While attempts to N-acylate compounds (1-3) intermolecularly with different acylating agents failed, intramolecular acylation of the carboxylic acid derivative 24 using trifluoromethanesulfonic anhydride and diisopropylethylamine at - 78°C succeeded, to give the 1,4-benzodiazepine 28. The intermediacy of the mixed sulfonic-carboxylic anhydride in this acylation reaction was strongly supported by the novel, direct acylation of benzene with benzoic acid under the same conditions. Relevant spectroscopic data of these new compounds are discussed.
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■ Formal Synthesis of the Indole Alkaloids Ngouniensine and Epingouniensine
M.-Lluïsa Bennasar, Ester Zulaica, Ramon Vila, and Joan Bosch*
*Laboratory of Organic Chemistry, Faculty of Pharmacy, University of Barcelona, Av. de Joan XXIII, s/n, 08028 Barcelona, Spain
Abstract
An alternative route to the tetracyclic ketones 9, key intermediates in our total synthesis of (±)-ngouniensine and (±)-epingouniensine, is reported.
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■ Reaction of Bis(3,3-dimethyl-2-oxobutyl)sulfide with Lawesson’s Reagent. Formation of 1,4-Di-t-butyl-2,5,7-trithia[2.2.1]heptane and 2,5- and 2,6-Di-t-butyl-1,4-dithiins
Juzo Nakayama,* Keum Soo Choi, Shoji Yamaoka, and Masamatsu Hoshino
*Department of Chemistry, Faculty of Science, Saitama University, Saitama, Saitama 338-8570, Japan
Abstract
Treatment of bis(3,3-dimethyl-2-oxobutyl) sulfide (1) with Lawesson’s reagent (3 equiv.) in refluxing toluene for 2 h affords 1,4-di-t-butyl-2,5,7-trithia[2.2.1]heptane (2) in 42% yield and 2,5- and 2,6-di-t-butyl-1,4-dithiins (3 and 4) in 43% yields in the 1:4 ratio.