HETEROCYCLES
An International Journal for Reviews and Communications in Heterocyclic ChemistryWeb Edition ISSN: 1881-0942
Published online by The Japan Institute of Heterocyclic Chemistry
Special Issue
Volume 50's Special Issues, Vol. 50, No. 2, 1999
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■ An Efficient Route to Formyldeuteroporphyrins and Their Wittig Reaction
Akira Ando, Miyuki Yamazaki, Mika Komura, Yuka Sano, Nami Hattori, Masaaki Omote, and Itsumaro Kumadaki*
*Faculty of Pharmaceutical Sciences, Setsunan University, 45-1, Nagaotoge-cho, Hirakata-shi, Osaka 573-0101, Japan
Abstract
Copper complex of deuteroporphyrin dimethyl ester (2) was formylated with trimethyl orthoformate in the presence of tin(IV) chloride, followed by demetallation with H2SO4-CF3COOH and separation by column chromatography to give 3- (5) and 8-formyl compounds (6) in 46 and 47% yields, respectively. The Wittig reaction of these formylporphyrins gave highly functionallized derivatives of porphyrin.
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■ Rearrangement Reaction of Tetrahydrofurans and Tetrahydropyrans Having a C1'-Mesyloxy Group on the C2-Side Chain with Zinc Acetate
Kazuo Nagasawa, Nobuyuki Hori, Hiroyuki Koshino, and Tadashi Nakata*
*The Institute of Physical and Chemical Research, Wako-shi, Saitama 351-0198, Japan
Abstract
Rearrangements of tetrahyrofurans and tetrahydropyrans having a C1'-mesyloxy group on the C2-side chain with zinc acetate in aq. AcOH were investigated. Rearrangement-ring expansion and/or rearrangement-ring opening reactions took place depending on the stereostructure of the substrates.
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■ Regioselectivity of 1,3-Dipolar Cycloaddition of 3-Oxidopyridinium Betaines to Olefins and Stereoselective Synthesis of 6-Alkyloxy-5-oxa-9-azatricyclo[5.2.1.04,8]decan-2-one Derivatives
François Estour, Stéphane Rézel, Didier Fraisse, Jacques Métin, Vincent Gaumet, Claire Lartigue, Gilles Miscoria, Alain Gueiffier, Yves Blache, Jean C. Teulade, and Olivier Chavignon*
*Départment d'Analyse Structurale et de Pharmacologie, Faculté de Pharmacie, UMR INSERM 484, 28 Pl. H. Dunant, B. P. 38, 63001 Clermont-Ferrand Cedex 1, France
Abstract
A new method to obtain the four isomers of tropane skeleton by dipolar addition of 3-oxidopyridinium betaines to activated olefins is described, and a general synthetic strategy for tricyclic tropane homologues is also reported.
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■ Preparation of 2-Alkylselenobenzothiazoles by the Reaction of Alcohols with 2-(2-Oxoethylseleno)benzothiazoles in the Presence of Tertiary Phosphines
Koichi Shibata,* Hiko Yamaga, and Oyo Mitsunobu*
*Department of Chemistry, College of Science and Engineering, Aoyama Gakuin University, 6-16-1 Chitosedai, Setagayaku, Tokyo 157-8572, Japan
Abstract
Reactions of alcohols with 2-(1,2-diphenyl-2-oxoethylseleno)benzothiazole in the presence of Bu3P gave the corresponding 2-alkyselenobenzothiazoles, where inversion of the secondary carbinol center of the alcohols took place. 1,3-Butanediol reacted at the primary hydroxyl group, while 1-phenyl-1,2-ethanediol reacted at the secondary hydroxyl group.
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■ A Concise Synthesis of (+)-α-Allokainic Acid via Site- and Diastereoselective Intramolecular C-H Insertion Process
Masahiro Anada, Tomohiro Sugimoto, Nobuhide Watanabe, Makoto Nakajima, and Shun-ichi Hashimoto*
*Graduate School of Pharmaceutical Science, Hokkaido University, Sapporo 060-0812, Japan
Abstract
A new route to (+)-α-allokainic acid commencing with L-serine has been established, wherein the key step involves a C3, C4 bond formation with a simultaneous creation of a C2,C3-trans and C3,C4-trans arrangement of substituents by Rh2(OAc)4-catalyzed C-H insertion reaction of α-diazoacetoacetamide tethered to (S)-4-(3-butenyl)-2,2-dimethyl-1,3-oxazolidine system. Taber's computaional model confirms the observed diastereomer preference.
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■ Synthesis of Solamin
Wataru Kuriyama, Ken Ishigami, and Takeshi Kitahara*
*Department of Applied Biological Chemistry, Graduate School of Agricultural and Life Sciences, The University of Tokyo, 1-1-1 Yayoi, Bunkyo-ku, Tokyo 113-8657, Japan
Abstract
Total synthesis of an annonaceous acetogenin, solamin (1) is described. Direct coupling between γ-lactone (13) and mono-THF unit (12) prepared from D-glutamic acid in 16 steps gave the product (14) in excellent yield, which was converted to the title compound (1) in sequential 3 steps.
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■ Dual p-Coumaroyl CoA Biosynthesis in Morus alba Cell Cultures
Yoshio Hano, Manabu Shimazaki, Taro Nomura,* and Shinichi Ueda
*Faculty of Pharmaceutical Sciences, Toho University, 2-2-1, Miyama, Funabashi, Chiba 274-8510, Japan
Abstract
Morus alba callus and cell suspension cultures specifically produce chalcomoracin (1) and kuwanon J (2) both originated from cinnamoylpolyketide intermediate. Administration of [2-13C]cinnamic acid N-acetylcysteamine thioester to the M. allba cell cultures revealed the cinnamoyl CoA intermediate to be a significant precursor. The present result, coupled with the parallel contribution of both L-phenylalanine and L-tyrosine to the same cinnamoyl part, gave a conclusive evidence for the route leading to p-coumaroyl CoA in the M. alba cell cultures.
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■ Diastereo- and Enantioselective Synthesis of Δ2-1,2,4-Oxadiazolines by 1,3-Dipolar Cycloaddition of Nitrile Oxides with Chiral Hydrazones
Dieter Enders,* Ilka Meyer, Jan Runsink, and Gerhard Raabe
*Institut für Organische Chemie, Rheinisch-Westfälische, Technische Hochsch, Professor-Pirlet-Strasse 1, D-52074 Aachen, Germany
Abstract
Diastereo- and enantioselective 1,3-dipolar cycloadditions of nitrile oxides (3) with α,β-unsaturated hydrazones (2) gave spiro oxadiazolines (4) in good yields and low to excellent diastereomeric excesses (de = 5->98%). Open chain hydrazones (6) afforded 5,5-disubstituted Δ2 -1,2,4-oxadiazolines (7). A subsequent N-N bond cleavage to remove the chiral auxiliary was achieved with formic acid and gave the oxadiazolines (8)(ee = 0 - 91%).
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■ The Efficient Synthesis of 1,2-Dioxetanes from Indene and 1,2-Dihydronaphthalene
Charles W. Jefford* and Marcelo Ferrufino Deheza
*Department of Organic Chemistry, Laboratory fo Crystallography, University of Geneva, 30, quai Ernest Ansermet, 1211 Geneva 4, Switzerland
Abstract
Indel (1), 1-methylindene (7), 2-methylindene (10), 1,2- and 1,4-dihydronaphthalenes (3 and 18) were converted into their trans-1,2-bromo-hydroperoxides. The latter on treament with a mixture of Ag2O/AgSO2CF3 in CH2Cl2 at room temperture gave the corresponding 1,2-dioxetanes in yields of 90,88,80,80, and 50% respectively. The cis-disposed bromo-hydroperoxide obtained from 7 was unreactive on treatment with the silver mixture. Similar treatment of the trans-bromo-hydroperoxide obtained from 3,3-dimethylindene (14) was equally without effect, no dioxetane being formed.
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■ Chiral Auxiliary Approach to the Asymmetric Pictet-Spengler Reaction of Tryptamines
Tomohiko Kawate, Masamichi Yamanaka, and Masako Nakagawa*
*Faculty of Pharmaceutical Sciences, Chiba University, 1-33 Yayoi-cho, Inage-ku, Chiba 263-8522, Japan
Abstract
The diastereoselective Pictet-Spengler reaction of chiral tryptamines bearing an α-naphthylethyl auxiliary group was investigated. In the presenceof trifluoroacetic acid as a catalyst, the Pictet-Spengler reaction of various aldehydes gave the corresponding tetrahydro-β-carbolines at a diastereoselectivity of up to 93 : 7.
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■ Peptide Coupling Reactions with Phosphono-Phosphino Substituted γ-Thiapyrones — First Step to Unusual Peptides
Dirk Uwe Hahn and Richard Neidlein*
*Pharmazeutisch-Chemishces Institut, Ruprecht-Karls-Universität Heidelberg, Im Neuenheimer Feld 364, D-69120 Heidelberg, Germany
Abstract
The reaction of phosphono-phosphino substituted γ-thiapyrones (8/9) with pentafluorphenyldiphenylphosphinate - FDPP - (7) and protected α-L-amino acids (10) lead to chiral α-peptido substituted phosphono-phosphino γ-thiapyrones (12/13). Besides β-peptido- and peptoido substituted phosphono γ-thiapyrones (16/21) are synthesized in the presence of FDPP as an efficient peptide coupling reagent.
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■ Synthesis of New Melatoninergic Ligands Including Azaindole Moiety
Daniel Mazéas, Gérald Guillaumet, and Marie-Claude Viaud*
*Laboratoire de Chimie Bioorganique et Analytique, associe au CNRS, Université d'Orléans, B.P. 6759, Rue de Chartres, 45067 Orleans Cedex 2, France
Abstract
A novel series of melatonin analogues, based on the azaindole nucleus is described. These compounds are prepared in several steps directly from the commercial available 7-azaindole or from substituted amino-, iodo- or/and nitropyridines using a catalysed palladium reaction or vicarious nucleophilic substitution of hydrogen (VNS) in order to elaborate the 6-, 5- and 4-azaindole derivatives derivatives respectively.
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■ A Convenient Approach to the Synthesis of the Imidazo[5,1-b]oxazole Ring System
Héctor Salgado-Zamora,* Elena Campos, Rogelio Jiménez, Esmeralda Sánchez-Pavón, and Humberto Cervantes
*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
Reaction of 4(5)-bromo-2-methyl-5(4)-nitroimidazol with phenacyl bromide derivatives led to 4-bromo-2-methyl-1-phenyl-1-phenacyl-5-nitro- and 5-bromo-2-methyl-1-phenacyl-4-nitroimidazoles. Treatment of the latter isomers with potassium tert-butoxide in dry THF yielded imidazo[5,1-b]oxazoles.
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■ Synthesis of a Novel Multi-Receptor Containing Hydrogen Bonding Sites and Ion Binding Sites
Tatsuya Nabeshima* and Takeshi Hanami
*Department of Chemistry, University of Tsukuba, 1-1-1 Ten-nodai, Tsukuba-shi, Ibaraki, 305-8571, Japan
Abstract
A new linear ditopic receptor (1) which contains two 2,6-diaminopyridine moieties and two 2,6-diaminopyridine moieties and two crown ether rings at the termini has been synthesized. The host (1) binds a thymine derivative and behaves as a ditopic receptor in a transpor in a transport experiment.
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■ Simple Syntheses of Thieno[4,3,2-d,e]isoquinoline-3,5-diones and Their Homologues
Ferenc Fülöp,* Bert Naumann, Gábor Günther, Gábor Bernáth, and Reijo Sillanpää
*Institute of Pharmaceutical Chemistry, Albert Szent-Györgyi Medical University, POB 121, H-6701 Szeged, Eötvös u. 6, Hungary
Abstract
Simple, convenient syntheses of thieno[4,3,2-d,e]isoquinoline-3,5-diones (7a-d) and their homologues (8a-c) were achieved strating from ethyl 2-amino-3-cyano-4,5,6,7-tetrahydrobenzo[b]thiophene-4-carboxylate (2) and its homologue derivatives (5) by sulfuric acid treatment.
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■ Synthetic Studies of Forskolin. A Formal Synthesis via a Nicolaou's Advanced Intermediate
Hsing-Jang Liu* and Xiao Shang
*Department of Chemistry, University of Alberta, Edmonton, Alberta, T6G 2G2, Canada
Abstract
A formal synthesis of (±)-forskolin (1) has been effected making use of enone (2) as a relay compound.
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■ Towards a Unitary Description of the Photochemical Isomerization Reactions in Pentaatomic Aromatic Heterocycles: The Case of Furan, Thiophene, Pyrrole, Isoxazole, Imidazole, and Pyrazole Derivatives
Maurizio D’Auria
*Dipartamento di Chimica, Università della Basilicata, Via N. Sauro 85, 85100 Potenza, Italy
Abstract
The photochemical behaviour of furan, thiophene, pyrrole, isoxazole, imidazole, and pyrazole, and pyrazole derivatives appears to be very complex and, apparently, no common description of the reactivity of these heterocycles is possible. On the basis of PM3-RHF-Cl semiempirical calculations an unitary description of the behaviour of theses molecules can be made.
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■ Diels-Alder Reactions of Benzo[b]furan-4,5-diones and Benzo[b]furan-4,7-diones
Pascal Nebois and Houda Fillion*
*Laboratoire de Chimie Organique, Institut des Sciences Pharmaceutiques et Biologiques, Université Claude Bernard, Lyon I, 8 avenue Rockfeller, 69373 Lyon Cedex 08, France
Abstract
The synthetic potentiality of benzofurandiones in Diels-Alder reactions is reported. Factors influencing the regiochemistry are discussed.
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■ 1-Hydroxyindoles
Masanori Somei*
*Faculty of Pharmaceutical Scicences, Kanazawa University, 13-1 Takara-machi, Kanazawa 920-0934, Japan
Abstract
This review summarizes our hypotheses, syntheses, physical and chemical properties, and chemical reactions of 1-hydroxyindoles. Syntheses of natural products having 1-methoxyindole nucleus 1-methyoxy derivatives of indole alkaloids are also included. Application of the chemistry of 1-hydroxyindoles to the syntheses of biologically active substances, syntheses of tryptophan-4,5-diones and their reactions, and biological evaluation of 1-hydroxyindoles are reviewed.
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■ 1,3-Dipolar Cycloadditions of Five and Six Membered Cyclic Nitrones to α,β-Unsaturated Acid Derivatives
Pedro de March,* Marta Figueredo, and Josep Font
*Departament de Química, Universidad Autònoma de Barcelona, 08193 Bellaterra (Barcelona), Spain
Abstract
The cycloadditions of 3,4-dihydro-2H-pyrrole 1-oxide, 3,4,5,6-tetrahydropyridine 1-oxide, and (S)-3,4-dihydro-2-hydroxymethyl-2H-pyrrole 1-oxide to α,β-unsaturated acid derivatives have been reviewed. As Z-olefins, several five, six, and seven membered lactones with different functionalization at the γ-position were employed. As E-olefins, γ-hydroxy-, γ-alkoxy-, and γ-oxo-α,β-unsaturated esters have been incorporated to this study. Steric factors play a very important role in the regio- and stereochemical outcome of these 1,3-dipolar cycloadditions. cis-Olefins yield products derived mainly from an exo transition state, while the cycloadducts of trans-olefins result mainly from endo approaches.
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■ Reactions of 1,4-Dichlorobut-2-yne Derivatives Leading to Heterocycles
Krishna C. Majumdar* and Paritosh Biswas
*Department of Chemistry, University of Kalyani, Kalyani-741 235, W. B., India
Abstract
This short review summarizes the syntheses of various types of chrom-3-ene derivatives by hydration of acetylenic linkage and polyheterocycles such as benzofuro[3,2-c]benzopyrans, benzofuro[3,2-b]benzofurans, benzofuro[2,3-b]benzofurans and a number of other heterocyclic systems by [3,3] sigmatropic rearrangements from 1,4-dichlorobut-2-yne derivatives.