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. 48, No. 7, 1998
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■ Product Structure as a Function of Reaction Conditions in the Reaction of Formaldehyde with an Alpha-Mercapto Amide
James D. Copp,* Francis O. Ginah, Marvin M. Hansen, Douglas P. Kjell, and Brian J. Slattery
*Chemical Process Research and Development Division, Lilly Reserach Laboratories, Eli Lilly & Company, Lilly Corporate Center, Indianapaolis, IN 46285-4813, U.S.A.
Abstract
Treatment of mercapto amide (3) with formaldehyde and acid or base results in products whose structures are a function of the reaction conditions. Lactone (8), hemithioacetal (9), and dimer (7) were formed in good yields under acidic reaction conditions. In addition, dienenone (10) was produced from the treatment of (9) with strongly coordinating Lewis acids. Treatment of (9) with NH3/MeOH gave the desired thiazolidinone (1) in moderate yield.
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■ Model Studies toward the Synthesis of Na-Acetyl-Nb-methylphlegmarine: Addition of Cyclohexylmethyl Organometallics to 1-Acylpyridinium Salts
Daniel L. Comins,* Chris J. Foti, and Adam H. Libby
*Department of Chemistry, North Carolina State Univesity, P. O. Box 8204, Raleigh, NC 27695-8204, U.S.A.
Abstract
Addition of various cyclohexylmethyl organometallics to a chiral 1-acylpyridinium salt was investigated as a model study toward the asymmetric synthesis of the Lycopodium alklaoid, phlegmarine (1d).
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■ Total Synthesis of Macrocyclic Antibiotic, Micrococcin P1
Kazuo Okumura, Akinori Ito, Dai Yoshioka, and Chung-gi Shin*
*Laboratory of Organic Chemistry, Faculty of Technology, Kanagawa University, 3-27-1 Rokkakubashi, Kanagawa-ku, Yokohama 221-8686, Japan
Abstract
Total synthesis of a macrocyclic antibiotic, micrococcin P1 (1), constructed from four segments called Fragmetns, A, B, C, and D, was achieved. The synthesis of a central 2,3,6-trithiazole-substituted pyridine moiety [Fragment A with C (A-C)], followed by coupling with Fragments B and D synthesized independently gave the protected Fragment A-B-C-D. Final deprotection of all the protecting gourps and cyclization gave synthetic 1.
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■ Stereocontrolled Synthesis of Tetrahydrofurans and Tetrahydropyrans by Cyclisation of Hydroxyselenides
Luca Arista, Michelangelo Gruttadauria,* and Renato Noto
*Dipartimento di Chimica Organica, Universita di Palermo, Via Archirafi 20 90123 Palermo, Italy
Abstract
An efficient stereocontrolled synthesis of 2,3,5-trisubstituted tetrahydrofuran and 2,4,6-trisubstituted tetrahydropyran rings from homoallylic alcohols (16) and (18) was achieved by: i) epoxidation; ii) ring opening of the epoxide with sodium phenyl selenide; iii) cleavage of the TBDMS group with a stereoconvergent elimination of water followed by intramolecular oxygen nucleophile capture. The presence of a branching near to the selenonium ring made the attack in the exo mode faster than the attack in the endo/exo mode.
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■ A Novel Synthesis of 1,3-Benzodiazepin-2-ones Using Intramolecular Heck Reaction
Masahito Hayashi, Hiroshi Sai, and Hiroshi Horikawa*
*Lead Optimization Research Laboratory, Tanabe Seiyaku Co.Ltd., 2-2-50, Kawagishi, Toddda, Saitama 335-8505, Japan
Abstract
The formation of the skeleton of 1,3-benzodiazepin-2-one could be efficiently achieved by intramolecular Heck reaction. This methodology was well applicable to the preparation of optically pure 4-substituted 1,3-benzodiazepin-2-ones starting from easily available α-amino acids.
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■ Synthesis and Reactions of Chiral Cyclic Nitrones Derived from D-Ribose
Cedric W. Holzapfel* and Renier Crous
*Department o f Chemistry and Biochemistry, Rand Afrikaans University, P.O. Box 524, Auckland Park, 2006, Johanesberg, South Africa
Abstract
A facile route to chiral cyclic nitrones derived from D-ribose is described. Their versatility as substrates for 1,3-dipolar cycloadditions and nucleophilic additions is demonstrated.
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■ Conambine, a New Norditerpenoid Alkaloid from Consolida ambigua Seeds
Haridutt K. Desai and S. William Pelletier*
*Institute for Natural Products Research and Department of Chemistry, The University of Georgia, Chemistry Building, AthensGeorgia 30602-2556, U.S.A.
Abstract
A new norditerpenoid alkaloid, "conambine" (1) has been isolated from the seeds of Consolida ambigua L. Its structure has been established on the basis of its spectroscopic data and chemical correlation with anthranoyllycoctonine (3).
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■ Synthesis and Stability of 5-, 7- and 8-Substituted Benzo-1,2,3,5-tetrazepin-4-ones
Bertrand J. Jean-Claude* and George Just
*Department of Chemistry, McGill University, 7 Montreal, Quebec H3A 2K6, Canada
Abstract
In order to determine the effect of substituents on the stability of benzo-fused 1,2,3,5-tetrazepin-4-ones, 5-,7- and 8-substituted derivatives (6a-d), and (10) were synthesized. The stability of the tetrazepinones increased with the electron withdrawing character of the substituents at the benzene ring. Bulky groups at the 5 position destabilize the tetrazepinone ring. The unstable tetrazepinones (6b, 10 and 14) decomposed in chloroform at room temperature to benzotriazole derivatives (11, 12, and 15). X-Ray diffraction of nitrobenzotetrazepinone (6d) showed that despite the electron withdrawing effect of the nitro group para to the triazene chain, N3 exhibited a significant pyramidal character. In 6d, the 1,2,3,5-tetrazepinone cycle has an almost perfect seven-membered ring boat shape.
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■ Synthesis of Furanonaphthazarin Derivatives
Ricardo A. Tapia,* Miriam C. Gárate, Jaime A. Valderrama, and Paul R. Jenkins
*Facultad de Química, Pontificia Universidad Católica de Chile, Casilla 306, Correo 22, Santiago, Chile
Abstract
A three-step synthesis of the 5,8-dihydroxy-2-(1-methylethyl)naphtho[2,3-b]furan-4,9-dione (9) starting from 2-hydroxy-5,8-dimethoxy-1,4-naphthoquinone (4), is described. Further treatment of (9) with selenium dioxide in the presence of pyridine N-oxide as co-oxidant gave 2-(1-hydroxy-1-methylethyl)naphtho[2,3-b]furan-4,9-dione (10).
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■ The Direct Synthesis of Isoflavans via α-Alkylation of Phenylacetates
Marietjie Versteeg, Barend C. B. Bezuidenhoudt, and Daneel Ferreira*
*Department of Chemistry, University of Orange Free State, P.O. Box 339, Bleoemfontien, 9300, South Africa
Abstract
Deprotonation of oxygenated phenylacetates and quenching of the enolates with oxygenated benzylic electrophiles, afforded 2,3-diarylpropanoates which served as precursors to the isoflavans following consecutive reduction and cyclization steps.
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■ Acylation of Guanylhydrazones Derived from Cyclic Ketones: Synthesis of 3-Acylamino-1-cycloalkenyl-5-methyl-1H-1,2,4-triazoles
Zoltan Györgydeák and Wolfgang Holzer*
*Institute of Pharmaceutical Chemistry, University of Vienna, Währinger Strasse 14, A-1090 Vienna, Austria
Abstract
Reaction of guanylhydrazones derived from different cycloalkanones, 1-indanone and 4-chromanone, respectively, with excessive acetic anhydride leads to the formation of 3-acetylamino-1-cycloalkenyl-5-methyl-1H-1,2,4-triazoles. However, with camphor guanylhydrazone only the corresponding N,N’-diacetylguanylhydrazone was obtained, whereas 2-adamantone guanylhydrazone afforded 2-(3-acetylamino-5-methyl-1,2,4-triazol-1-yl)-2-adamantyl acetate. Detailed NMR spectroscopic studies (1H, 13C) with the title compounds and their guanylhydrazone precursors are presented.
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■ Transformation of Oxomethanobenzocyclooctenecarboxylic Acids to Pyrrolidinone-fused Penta-, Hexa- and Heptacyclic Hetero Compounds
Ferenc Miklós, Géza Stájer,* Pál Sohár, Gábor Bernáth, and Reijo Sillanpää
*Institute of Pharmaceutical Chemistry, Albert Szent-Györgyi Medical University, POB 121, H-6701 Szeged, Eötvös u. 6, Hungary
Abstract
10-Oxo-5r,6,7,8c,9c,10-hexahydro-5,9-methanobenzocyclooctene-8-carboxylic acid (1a) or a C-8 epimeric mixture (1a and 1b) reacted with 1,2-, 1,3- and 1,4-bifunctional reagents, 1,2- or 1,3-diaminopropane (2, 3), 1,2- or 1,3-propanolamine (4, 5), 1,4-diaminobutane (6), o-aminothiophenol (7), diexo-3-aminobicyclo[2.2.1]heptane-2-methanol or diendo-3-aminobicyclo[2.2.1]hept-5-ene-2-methanol (8, 9), to produce polycyclic compounds containing a pyrrolo-condensed pyrimidine (10), imidazole (11), 1,3-oxazine (12, 16, 17), oxazole (13), 1,3-diazepine (14), benzthiazole (15) moiety and one or two terminal aromatic rings by cyclization. The structures of 10-17 were established by 1H and 13C NMR spectroscopy and for 16 also by X-Ray analysis.
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■ Preparation and Absorption Spectral Properties of the Nitrogen Analogs of a Pechmann Dye and Its Isomeric Pyrano[4,3-c]pyran-1,5-dione
Hajime Irikawa,* Norihide Adachi, and Hirokazu Muraoka
*Department of Chemisttry, Faculty of Science, Shizuoka University, Ohya, Shizuoka 422-8529
Abstract
Bathochromic shifts were observed by replacement of the lactone-oxygen atoms in a Pechmann dye with nitrogen atoms, while hypsochromic shifts were caused by replacement of the lactone-oxygen atoms in a pyrano[4,3-c]pyran-1,5-dione with nitrogen atoms.
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■ Synthesis and Antitumoral Evaluation of 12-Substituted 6,7-Dihydrobenzo[4,5]-cyclohept[1,2-b]indole Derivatives
Benoît Joseph, Virginie Chapellier, Jean-Yves Mérour,* and Stéphane Léonce
*Instiut de Chimie Organique et Analytique, U. F. R. de Sciences, Université d'Orléans, BP 6759, Rue de Chartres, 45067 Orleans Cedex 2, France
Abstract
The synthesis of 12-substituted 6,7-dihydrobenzo[4,5]cyclohept[1,2-b]indole derivatives (2-3) are described. The antiproliferative activity of some of them were evaluated.
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■ Synthesis, 1H and 13C NMR Spectra, and Configurational Assigment of Furfurylideneimidazolinones
Peter Schuisky, Wolfgang Twistel, and Spiros Grivas*
*Department of Organic Chemistry, Södertörn University College, Karolinska Institutet, Novum Research Park, SE-141 57 Huddinge, Sweden
Abstract
The title compounds (14 and 15) were obtained by the condensation of a 2- or 3-furaldehyde derivative (prepared from 2-methylfuran) with 2-amino-1-methyl-2-imidazolin-4-one (6) or 5-one (7). Most products from 6 contained the (E)- and (Z)-isomers in comparable amounts; in those from7, the (Z)-isomer generally predominated. The isomers were distinguished by their 1H and 13C NMR spectra, in particular by the three-bond coupling between the carbonyl carbon and the olefinic hydrogen. This led to configurational reassignment of some previously reported analogues.
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■ Amine N-Oxides Derived from Alkaloids as Chiral Promoters in Enantioselective Pauson-Khand Reactions
Volker Derdau, Sabine Laschat,* and Peter G. Jones
*Institut für Organische Chemie, Technische Universität Braunschweig, Hagenring 30, D-38106 Braunschweig, Germany
Abstract
The novel indolizino[3,4-b]quinoline N-oxide (12) was prepared and characterized by X-Ray crystal structure determination. Compound (12) and sparteine N-oxides (8 - 10) were employed as chiral promoters in the Pauson-Khand cocyclization of various alkynes (1) with norbornene (4) to the bicyclic cyclopentenones (6) with enantioselectivities up to 33 %ee.
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■ Oxidation of 1,3-Dimethylthymine and 1,3-Dimethyluracil with Oxone® in the Solid to Solid State
Yongrae Hong, Soonjae Chang, Bosup Hahn,* and Fumio Toda
*Department of Chemistry, Ajou University, 5 Wonchun, Suwon 442-749, Korea
Abstract
The oxidation of the title substrates with Oxone® in the presence of camphor in the solid to solid state afforded a simple and efficient method for epoxidation under mild reaction condition.
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■ Axinellamines A and B, New Pyrrole Alkaloids of the Marine Sponge Axinella Sp.
Karen C. Bascombe, Sonia R. Peter, Winston F. Tinto,* Suzanne M. Bissada, Stewart McLean, and William F. Reynolds*
*Laboratory of Bioorganic Chemistry, Department of Biological Chemical Sciences, University of the West Indies, Cave Hill Campus, P.O. Box 64, Bridgetown, Barbados, West Indies
Abstract
Two new pyrrole alkaloids, axinellamines A and B, were isolated from the Caribbean marine sponge Axinella sp. and their structures were established on the basis of spectroscopic data, including 2D NMR spectroscopy. Axinellamine A was determined to be 2-((E,E)-6-methyl-2,4-octadienyl)pyrrole while axinellamine B was a dimer of axinllamine A, but containing an additional Me2C unit between the C-5 and C-5’ carbons of the two pyrrole rings.
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■ Caesalpinin B, a Rearranged Cassane Furanoditerpene of Caesalpinia bonduc
Deon L. Lyder, Winston F. Tinto,* Suzanne M. Bissada, Stewart McLean, and William F. Reynolds*
*Laboratory of Bioorganic Chemistry, Department of Biological Chemical Sciences, University of the West Indies, Cave Hill Campus, P.O. Box 64, Bridgetown, Barbados, West Indies
Abstract
A new rearranged cassane furanoditerpenone, caesalpinin B, was isolated from the roots of Caesalpinia bonduc, collected in Barbados, West Indies. The structure was established on the basis of spectroscopic data, including 2D NMR spectroscopy.
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■ Kinetic Resolution of Aryl Glycidyl Ethers: A Practical Synthesis of Optically Pure β-Blocker—S-Metoprolol
Mukund K. Gurjar,* Kashinath Sadalapure, Susanta Adhikari, Bugga V. N. B. S. Sarma, Arindam Talukdar, and Mukund S. Chorghade
*Organic Chemistry Division III, Indian Institute of Chemical Technology, Hyderabad 500 007, India
Abstract
Kinetic resolution of (±)-aryl glycidyl ethers using (R,R)-salen Co(III)OAc and water provided enantiomerically pure arylglycidyl ether and 1-arylglycerol derivatives with high enantiomeric excess. Application of this approach to (S)-metoprolol has been described.
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■ Synthesis, Complexation and Emission Behavior of N,N',N'',N'''-Tetrakis-(1-naphthylmethyl)-1,4,8,11-tetraazacyclotetradecane
Kanji Kubo,* Emi Yamamoto, and Tadamitsu Sakurai
*Instituete of Advanced Material Study, Kyushu University, 6-1, Kasuga-koen, Kasuga 816-8580, Japan
Abstract
Cyclam derivative (2) having four naphthylmethyl pendants was found to display unique photophysical properties in the presence of the guest metal salts. The fluorescence of the cyclam (2) was enhanced with various metal salts. The photoinduced electron transfer (PET) sensor (2) exhibited high Zn2+ selectivty.
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■ Biomimetic Formation and Interconversion in the Heteroyohimbine Series
Mauri Lounasmaa* and Pirjo Hanhinen
*Laboratory for Organic and Bioorganic Chemistry, Technical University of Helsinki, P.O. Box 6100, FIN-02150 HUT Espoo, Finland
Abstract
A general scheme, based on three currently accepted transformation reactions, is proposed for the biomimetic formation and interconversion of the four possible Δ20(21)-didehydroheteroyohimbines (cathenamines)(4, 9-11). The reactions permit, after reduction, access to all eight basic heteroyohimbine alkaloids (6-8, 12-16).