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. 9, 1993
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■ Synthesis of Mercurophilic Dicyanoheptafulvenes by Remote Substitution of 5,8,11,14,17-Pentaoxa-2,20-dithiabicyclo[19.4.1]hexacosa-21,23,25-trien-26-one and Its Homologues with Malononitrile
Kanji Kubo, Akira Mori, and Hitoshi Takeshita*
*Instituete of Advanced Material Study,86 Kyushu University, 6-1, Kasuga-koen, Kasuga 816-8580, Japan
Abstract
5,8,11,14,17-Pentaoxa-2,20-dithiabicyclo[19.4.1]hexacosa-21,23,25-trien-26-one and its homologs gave, via remote substitution, dithio-crown-etherated 8,8-dicyanoheptafulvene derivatives upon heating in acetic anhydride. The dithiocrown-etherated dicyanoheptafulvenes efficiently extract and reversibly transport Hg++ ion.
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■ Synthesis of Original Pyrrolonaphthyridines by 1,3-Dipolar Cycloaddition Reactions of Naphthyridinium Dicyanomethylides with Dimethyl Acetylenedicarboxylate
Isabelle Cardinaud, Alain Gueiffier,* Florence Fauvelle, Jean-Claude Milhavet, and Jean-Pierre Chapat
*Laboratoire de Chimie Organique Pharmaceutique, URA-CNRS, Faculté de Pharamcie, Université Montpellier I, 15, Avenue Charles Flahault, 34060 Montpellier, France
Abstract
The pyrrolo[2,1-f][1,6]naphthyridine, pyrrolo[1,2-a][1,8]- and [1,5]naphthyridines along with their corresponding 2,3- and 1,2-dihydrocompounds are synthesized from naphthyridinium dicyanomethylides and dimethyl acetylenedicarboxylate.
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■ Novel Heterocyclic Outer-Ring Dienes: N-Alkyl- and N-Aryl Substituted 4,5-Dimethylene-2-oxazolidinones
Raúl Hernández, José M. Sánchez, Adriana Gómez, Gonzalo Trujillo, Rossana Aboytes, Gerardo Zepeda, Roderick W. Bates, and Joaquín Tamariz*
*Departamento de Químíca Orgánica, Escuela Nacional de Ciencias Biológicas, I. P. N., Prol. Carpio y Plan de Ayala S/N,11340, Mexico, D.F.
Abstract
The one-pot synthesis of the hitherto unknown N-substituted 4,5-dimethylene-1,3-oxazolidin-2-ones from diacetyl and the corresponding isocyanate in the presence of triethylamine is described. Diene (4a) undergoes Diels-Alder cycloaddition with N-phenylmaleimide (10), and, in the absence of a dienophile, gives a mixture of dimers (12) and (13), and the ring closure cyclobutene (14).
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■ Total Synthesis of (±)-Cembranolide via Cr(II) Mediated Intramolecular Macrocyclization of β-Alkoxycarbonylallyl Halide
Kiyoshi Nishitani, Toshihiko Konomi, Youji Mimaki, Takashi Tsunoda, and Koji Yamakawa*
*Faculty of Pharmaceutical Sciences, Science University of Tokyo, 12, Ichigaya Funagawara-machi, Shinjuku-ku, Tokyo 162-0826, Japan
Abstract
The ω-formyl-β-methoxycarbonylallyl halide (20), prepared from geraniol and methyl β-hydroxypropionate, was cyclized efficiently and with high stereoselectivity to 14-membered cis-cycloalkenol (21) by CrCl2 in DMF. The cycloalkenol was treated with p-TsOH to give an excellent yield of (±)-cis-cembranolide (IV).
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■ Reactions of 2-Amino-1-azaazulenes with Diphenylcyclopropenone
Noritaka Abe* and Akikazu Kakehi
*Department of Chemistry, Faculty of Science, Yamaguchi University, 1677-1 Yoshida, Yamaguchi 753-8512, Japan
Abstract
Reaction of 2-amino-1-azaazulene with diphenylcyclopropenone gave 1,2-diphenyl-1,2,3,10b-tetrahydro-4,10b-diazabenz[a]azulen-3-one, which rearranged to N-(1-azaazulen-2-yl)-α-cis-stylbenecarboxamide and N-(1-azaazulen-2-yl)-α-trans-stylbenecarboxamide by heating. Some structures of these products were determined by the X-ray structure analyses. The reaction mechanism is discussed.
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■ Stereocontrolled Formation of Functionalized erythro-1,2-Diols via Hydroboration of 2-Alkyl-4,5-dihydrofurans
Roger Amouroux,* Abdelmalik Slassi, and Christine Saluzzo
*Laboratoire de Chimie Organique Physique et Synthétique, Associe au CNRS, Université Claude Bernard, Lyon 1, 43, Bd du 11 Novembre 1918 69622 Villeurbanne Cedex, France
Abstract
trans-2-Alkyl-3-hydroxytetrahydrofurans, prepared by the stereospecific hydroboration / oxidation reaction of 2-alkyl-4,5-dihydrofurans, were regioselectively cleaved with (CH3)3SiCl/NaI to afford 1-iodo-erythro-3,4-diols in CH3CN or the corresponding acetonide derivatives in CH3COCH3.
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■ N-Demthylation Studies of Pavine Alkaloids
Shoei-Sheng Lee,* Yi-Chu Liu, Shu-Hwei Chang, and Chung-Hsiung Chen
*School of Pharmacy, National Taiwan University, 1, Jen-Ai Road, Section 1, Taipei 10018, Taiwan, R.O.C.
Abstract
The N-norpavines, ring homologues of MK-801— a potent NMDA receptor antagonist, were prepared from N-methyl quaternary pavines by two nucleophilic reaction steps: N-methyl quaternary ammonium salts into tertiary amine by reacting with NaHTe (ethanolamine/δ or OAc- salt/DMF, δ); tertiary amine into N-norpavines by the von Braun reaction and subsequent hydrolysis.
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■ The Diels-Alder Reaction of Pyridazinones as Dienophiles
Péter Mátyus,* Kaoru Fuji, and Kiyoshi Tanaka*
*Institute for Chemical Research, Kyoto University, Uji, Kyoto 611-0011, Japan
Abstract
The Diels-Alder reaction of 5-iodo- (1a) and 5-ethylsulfonyl-2-methyl-3(2H)-pyridazinone (1b) with 2,3-dimethyl-1,3-butadiene afforded phthalazinone (3) and dihydrophthalazinone (2) as isolable products, respectively. The cycloadditions are well interpreted by the theoretical considerations based on the calculated AM1 data.
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■ Synthesis of N-(2-Dialkylaminoethyl)-2-oxo-2H-1-benzo(thio)pyran-3-carboxamidines
Youssef El-Ahmad, Jean-Daniel Brion,* and Pierre Reynaud
*Laboratoire de Chimie Thérapeutique, UFR des Sciences Pharmaceutiques, 1, rue G. Veil, 44035 Nantes Cedex, France
Abstract
An improved method for the preparation of N-(2-dialkylaminoalkyl)substituted 2-oxo-2H-benzo(thio)pyran-3-carboxamidines from the corresponding methyl(thio)coumarin-3-carboximidothioates is described.
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■ Monoacetoxylation of Methylenedioxy Groups in Dimethyl 4,4’-Dimethoxy-2,3,2’,3’-bismethylenedioxy-1,1’-biphenyl-6,6’-dicarboxylate with Lead Tetraacetate
Masayuki Kimura,* Yoshiyuki Matsuoka, and Kunio Hosaka
*Tsumura Reserach Institute for Biology and Chemistry (TRIBIC), Tsumura & Co., 3586 Yoshiwara, Ami-machi, Inashiki-gun, Ibaraki 300-1192, Japan
Abstract
The utility of lead tetraacetate as a reagent for the monoacetoxylation of a methylenedioxy group in dimethyl 4,4’-dimethoxy-2,3,2’,3’-bismethylenedioxy-1,1’-biphenyl-6,6’-dicarboxylate (1a) is demonstrated. Mechanistic feature of the monoacetoxylation is discussed.
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■ Reactions of Tosylhydrazones of 2-Methoxy-1-azaazulene-3-carboxaldehyde and Azulene-1-carboxaldehyde with Styrenes and Stilbenes
Katsuhiro Saito,* Hiroshi Fushihara, Kiichiro Tominaga, Kyoko Kumagai, Satoru Kondo, Kunihide Fujimori, Noritaka Abe, and Kensuke Takahashi
*Department of Applied Chemistry, Nagoya Institute of Technology, Gokiso-cho, Showa-ku, Nagoya 466-8555, Japan
Abstract
The reactions of sodium salt of 2-methoxy-1-azaazulene-3-carboxaldehyde tosylhydrazone with styrenes gave 3,8-cyclohexeno-2-methoxy-1-azaazulenes and 3-cyclopropyl-2-methoxy-1-azaazulenes. The formers were afforded through the diazo compound generated from the tosylhydrazone and the latters were yielded via the carbene derived from the diazo compound. The reactions with stilbenes gave the corresponding cyclopropane derivatives. The similar reactions with sodium salt of azulene-1-carboxaldehyde tosylhydrazone gave the analogous result.
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■ Functionalized γ-Lactones via Intramolecular Nitrile Oxide Cycloaddition
Giuseppe Buemi, Ugo Chiacchio,* Antonino Corsaro, Giovanni Romeo, Antonio Rescifina, Nicola Uccella, and Alfred Hassner*
*Department of Chemistry, Bar-Ilan University, Ramat-Gan 52900, Israel
Abstract
The intramolecular nitrile oxide cycloaddition of a series of unsaturated hydroxyimino esters has been investigated. The reaction has been found to be stereospecific, with the configuration of the reacting double bond maintained in the final product. Lack of intramolecular pathway has been observed when R, R1 or R2 are hydrogen atoms. AM1 calculation help rationalizes the observed reactions.
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■ Regioselective Enzyme-catalyzed Synthesis of Pyrazole-containing Podands
Marta Flerros, María Isabel Rodríguez-Franco, Pilar Navarro, and Santiago Conde*
*Instituto de Química Médica, C. S. I. C., Calle Juan de Cierva, 3, 28006 Madrid, Spain
Abstract
Initial results are described about a new synthesis of a family of the acylic cation-complexing compounds named podands containing a pyrazole moiety as a part of the molecule. This synthesis was carried out by lipase-catalyzed transesterification of the corresponding pyrazole-3,5-dicarbethoxy derivative with di- and triethyleneglycol monomethylether; it afforded good yields and a high degree of regioselectivity in N-substituted pyrazoles where 3 and 5 positions are not equivalents. As an initial approach, a simpler model of transesterification with n-octanol was studied.
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■ Synthesis of (2R, 3S,4R)-3,4-Dihydroxy-2-hydroxymethylpyrrolidine and (2S,3R,4S,5S)-3,4-Dihydroxy-2,5-dihydroxymethylpyrrolidine from (R)-Serine and D-Ribonolactone
Nobuo Ikota
*National Institute of Radiological Sciences, 9-1, Anagawa-4-Chome, Inage-ku, Chiba 263-0024, Japan
Abstract
(2R,3S,4R)-3,4-Dihydroxy-2-hydroxymethylpyrrolidine derivative (9, 10) and (2S,3R,4S,5S)-3,4-dihydroxy-2,5-dihydroxymethylpyrrolidine derivatives (16, 17) were synthesized stereoselectively from (R)-serine and D-ribonolactone, respectively.
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■ Amidomercuration-Cyclization of N-tert-Butoxycarbonyl-2-allylaniline Derivatives
Jacob Berger* and Deborah L. Kerly
*Institute of Organic Chemistry, Syntex Discovery Research, 3401 Hillview Avenue, Palo Alto, California 94304, U.S.A.
Abstract
Dilithation of N-tert-butoxycarbonylanilines with tert-butylithium followed by addition of 4-bromo-2-methyl-2-butene affords N-tert-butoxycarbonyl-2-(3,3-dimethylallyl)anilines (3a-e). The mercuric ion-initiated cyclization of compounds (3a-e) was investigated. N-tert-Butoxycarbonyl-4-chloro-2-(3-methyl-2-buten-1-yl)aniline (3b) and the 6-fluoro analogue (3c) readily undergo amidomercuration-cyclization to give N-tert-butoxycarbonyl-5-chloro-2,2-dimethyl-1,2,3,4-tetrahydroquinoline (4b) and N-tert-butoxycarbonyl-8-fluoro-2,2-dimethyl-1,2,3,4-tetrahydroquinoline (4c). Anilides (3a, 3d-e) gave a mixture of tetrahydroquinolines (4a, 4d-e) and the dihydroindoles (5a, 5d-e). N-Ethoxycarbonyl-2-(3-methyl-2-buten-1-yl)aniline (3f) gave mainly the N-ethoxycarbonyl-2,2-dimethyl-1,2,3,4-tetrahydroquinoline (4f).
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■ Pyrrolo[1,2-a]thieno[3,2-f][1,4]diazepines: An Efficient Synthesis
Isabelle Rault, Marie-Paule Foloppe, Sylvain Rault, and Max Robba*
*Centre d’Etudes et de Recherch sur le Medicament de Normandie, Université de Caen, 1, rue Vaubénard, 14032 Caen Cedex, France
Abstract
Synthesis of pyrrolo[1,2-a]thieno[3,2-f][1,4]diazepines from 2-(1-pyrrolyl)thien-3-ylphenylmethylenimine is described.
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■ A New Route towards 8-Oxoprotoberberines
Teresa Vicente, Eduardo Martínez de Marigorta, Esther Domínguez,* Luisa Carrillo, and Dolores Badía
*Department of Organic Chemistry, Faculty of Sciences, University of Basque Country, P.O. Box 644, 48080 Bilbao, Spain
Abstract
A new and short route for the preparation of 5-hydroxy-8-oxoprotoberberines and their conformational analysis are reported.
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■ Synthesis of (-)-Heliotridane and (-)-Isoretronecanol via Diastereoselective Conjugate Addition of Organocuprates to an Enoate Deriving from Proline
Sylvie Le Coz, André Mann,* Frédéric Thareau, and Maurizio Taddei
*Laboratoire de Pharmacochimie Moléculaire, Centre de Neurochimie du CNRS, 5, rue Blaise Pascal, 67084 Strasbourg Cedex, France
Abstract
A syntesis of the pyrrolizidine alkaloids (-)-heliotridane and (-)-isoretronecanol and their epimers is described. The key step involves a diastereoselective conjugate addition of organocuprates to (2S)-N-(tert-butoxycarbonyl)-2-[(E)-3’-methoxy-3’-oxo-1’-propenyl]pyrrolidine (2) deriving from (S)-proline.
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■ Two New Lignan Glucosides from Arum italicum
Marina Della Greca, Antonio Molinaro, Pietro Monaco, and Lucio Previtera*
*Dipartimento di Chimica Organica e Biologica, Università Federico II, Via Mezzocannone 16, I-80134 Napoli, Italy
Abstract
Two new lignan glucosides, namely (+)-lariciresinol 4’-O-β-D-glucopyranoside and (+)-lariciresinol 9-O-β-D-glucopyranoside, besides ferulic acid, coniferyl alcohol 4-O-β-D-glucopyranoside, 4-coumaryl alcohol 4-O-β-D-glucopyranoside, (+)-pinoresinol-O-β-D-glucopyranoside, (+)-syringaresinol-O-β-D-glucopyranoside, (+)-lariciresinol and (+)-lariciresinol and (+)-lariciresinol 4-O-β-D-glucopyranoside, have been isolated and characterized as peracetyl derivatives from Arum italicum.
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■ Diastereoselective Conjugate Addition Approach to Picenadol and Oxygenated Analogues
Michael J. Martinelli,* Barry C. Peterson, and Darrell R. Hutchison
*Lilly Reserach Laboratories, A Division of Eli Lilly & Company, Lilly Corporate Center, Indianapolis, IN 46285-4813, U.S.A.
Abstract
Horner-Emmons-Wadsworth reaction with 1,3-dimethyl-4-piperidone in water afforded and exocyclic enone, whith minimal deconjugation of the double bond. Copper catalyzed conjugate addition with an aryl Grignard reagent then afforded an adduct with high stereocontrol. Wolff-Kischner reduction and deprotection proceeded to provide picenadol (1) in excellent overall yield. Access to oxygenated analogues of picenadol was also accomplished with this approach.
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■ An Unusual Acid-catalyzed Rearrangement of 1,2,4-Trioxanes
Yu-MIng Pu, Herman Yeh, and Herman Ziffer*
*National Instutute of Health, 9000 Rockville Pike, Bethesda, MD 20892-0815, U.S.A.
Abstract
A new Lewis acid-catalyzed rearrangement of the peroxide group in two 1,2,4-trioxanes, deoxoartemisinin and 12β-allyldeoxoartemisinin, yielding ring enlarged oxide, is described.
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■ A Regiospecific Synthesis of Highly Substituted Acridones
Colette Mongrain and Paul Brassard*
*Département de Chimie, Université Laval, Cité Universitaire, Québec, G1K 7P4, Canada
Abstract
The regiospecific substitution of isomeric halogenoquinones by the appropriate sulfonamide can be carried in the presence of fluoride ions and affords the corresponding o-methoxycarbonylanilinoquinones of definite structure. After reductive methylation, saponification and cyclization, these substrates provide ready access to highly substituted acridones and benz[b]acridones some of which are difficultly obtained by other means.
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■ An Efficient Synthesis of New Phenylpyrrolizine and Phenylpyrrolopyrazine Derivatives
Olivier Norbert Tembo, Patrick Dallemagne, Sylvain Rault, and Max Robba*
*Centre d’Etudes et de Recherch sur le Medicament de Normandie, U. F. R. des Sciences Pharmaceutiques, 1, rue Vaubénard, 14032 Caen Cedex, France
Abstract
Synthesis of new 3-phenyl-2,3-dihydro-1H-pyrrolizine derivatives is achieved starting from 3-amino-3-phenylpropionic acid via an iminium salt. The reactivity of this system is studied and the new 4-phenyl-1,2,3,4-tetrahydropyrrolo[1,2-a]pyrazin-1-one derivatives are synthesized, via a Beckmann’s rearrangement.
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■ Thermal Cycloaddition of Aroylketene to 1-Aryl-1-trimethylsilyloxyethylene: A Simple Synthesis of 2,6-Diaryl-4H-pyran-4-one
Takehiro Sano,* Toshiaki Saitoh, and Jun Toda
*Showa college of Pharmaceutical Sciences, 3-3165, Higashi-tamagawagakuen, Machida, Tokyo 194-8543, Japan
Abstract
Aroylketene (2) generated by pyrolytic decarbonylation of 5-aryl-2,3-dihydro-2,3-furandione (1) reacted with 1-aryl-1-trimethylsilyloxyethylene (3) in a regioselective manner to give 2,6-diaryl-4H-pyran-4-one (5) and/or 1,5-diarylpentane-1,3,5-trione (6). This reaction provides a simple synthetic method of 2,6-diaryl-4H-pyran-4-one with various substituents in the aryl goup.
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■ Oxidative Coupling of 4-Substituted N,N-Dimethylanilines with N-Substituted Maleimides in the Presence of Manganese(II) Nitrate under Oxygen
Satoru Murata, Koji Teramoto, Masahiro Miura,* and Masakatsu Nomura
*Department of Applied Chemistry, Faculty of Engineering, Osaka University, 2-1 Yamadaoka, Suita, Osaka 565, Japan
Abstract
The reaction of 4-substituted N,N-dimethylanilines with N-substituted maleimides proceeds in the presence of a catalytic amount of manganese(II) nitrate under oxygen to give the corresponding N-substituted 1,2,3,4-tetrahydro-1-methylquinoline-3,4-dicarboximides along with N-methylanilines