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. 63, No. 5, 2004
Published online: 24th February, 2004
■ Formation of 3-Pyrrolin-2-ones via 5-Endo-trig Cyclization
Ruri Naitoh, Yayoi Nakamura, Emi Katano, Yohoko Nakamura, Emi Okada, and Morio Asaoka*
*Department of Chemical and Biological Sciences, Faculty of Science, Japan Women’s University, 2-8-1 Mejirodai, Bunkyoku, Tokyo 112-0015, Japan
Abstract
Anionic cyclization of N-benzyl-3-phenylsulfanyl-2-propenamide derivatives gave the corresponding 3-pyrrolin-2-ones. Mechanistic investigation using deuterated starting materials revealed this cyclization proceeds via a 5-endo-trig process.
Published online: 12th March, 2004
■ Convenient Synthesis of Pulchellalactam, a CD45 Protein Tyrosine Phosphatase Inhibitor from the Marine Fungus Corollospora pulchella, and Its Related Compounds
Jun-ichiro Bessho, Yasuhiko Shimotsu, Sachiko Mizumoto, Nobuyuki Mase, Hidemi Yoda, and Kunihiko Takabe*
*Department of Molecular Science, Faculty of Engineering, Shizuoka University, 3-5-1 Johoku, Hamamatsu 432-8561, Shizuoka, Japan
Abstract
Convenient synthesis of pulchellalactam (1a) and its related compounds was accomplished. Total yields of (Z)-pulchellalactam and (E)-pulchellalactam were 55% for 5 steps and 43% for 8 steps from commercially available and inexpensive citraconic anhydride, respectively.
Published online: 8th March, 2004
■ Palladium(II)-catalyzed Stereocontrolled Cyclization via Hemiacetal Intermediates: Total Synthesis of 5-Epi-prelactone C
Masahiro Miyazawa, Magsarjav Narantsetseg, Hajime Yokoyama, Seiji Yamaguchi, and Yoshiro Hirai*
*Department of Chemistry, Faculty of Science, Toyama University, Gofuku 3190, Toyama 930, Japan
Abstract
Palladium(II)-catalyzed cyclization of 3,7-dihydroxy-4-methyl-5-octenal derivative was carried out to give 2,3,4,6-tetrasubstituted tetrahydropyran with stereoselective 1,3-chirality transfer in net retention of stereochemistry. The cyclized product was converted into 5-epi-prelactone C.
Published online: 26th March, 2004
■ A Novel Secondary Metabolite from Lethariella sernanderi
Kaoru Kinoshita, Kazuhiko Takatori, Takao Narui, Chicita F. Culberson, Masahiro Hasumi, Yuuichi Nishino, Kiyotaka Koyama, and Kunio Takahashi*
*Meiji Pharmaceutical University, 2-522-1 Noshio, Kiyose, Tokyo 204-8588, Japan
Abstract
A novel secondary metabolite, named sernanderin (1), was isolated from a lichen thallus, Lethariella sernanderi. The structure was elucidated on the basis of spectroscopic data, especially 2D-NMR spectrum and X-Ray crystallographic analyses. This compound (1) has a new skeletone as a natural product so far reported.
Published online: 24th February, 2004
■ Palladium-catalyzed Cyclocarbonylation of Unsaturated Alcohols and Amines. Chemoselective Synthesis of Heterocycle-substituted γ- and δ-Lactones and Lactams
Catia Granito, Luigino Troisi,* and Ludovico Ronzini
*Department of Sciences and Biological and Environmental Technologies, University of Lecce, Via Prov.le Lecce-Monteroni, 73100 Lecce, Italy
Abstract
Unsaturated alcohols and amines react with carbon monoxide and hydrogen, in the presence of a catalytic amount of palladium acetate and a phosphine ligand, to afford selectively heterocycle-substituted γ- and δ-lactones and lactams. The distribution of five- and six-membered ring compounds can be modulated by an appropriate combination of solvent and phosphine ligand. The five-membered products are formed in two isomeric forms trans and cis with a modest diasteroselectivity (trans>cis).
Published online: 8th March, 2004
■ Synthesis of 3-Ferrocenyl-3,3a,4,5-tetrahydro-2H-benzo[g]indazoles
Elena Klimova, Tatiana Klimova,* Teresa Ramírez Apan, Antonio Neito Camacho, Rafael Moreno Esparza, Carlos Damian Zea, and Marcos Martínez García
*Faculty of Chemistry, National Autonomous University of Mexico, Cd. Universitaria, Coyoacan, C.P. 04510, Mexico
Abstract
The reactions of E-2-ferrocenylmethylidenetetralones with hydrazine proceed diastereoselectively, forming the cis isomers of diazatricycles in high yields. The studies of the anti-inflammatory activity of E-2-ferrocenylmethylidenetetralones and N-acetylindazoles showed a moderate activity in a TPA model. The structure of 2-acetyl-3-ferrocenyl-6-methoxy- 3,3a,4,5-tetrahydro-2H-benzo[g]indazole was confirmed by X-Ray diffraction analysis.
Published online: 5th March, 2004
■ KF-Alumina Immobilized in Ionic Liquids: A Novel Heterogeneous Base for Heterocyclization of Alkylsulfanylphenylamines into 1,4-Benzothiazine
Bhupender S. Chhikara, Anil K. Mishra, and Vibha Tandon*
*Dr. B. R. Ambedkar Center for Biomedical Research, University of Delhi, Delhi-110 007, India
Abstract
A rapid and convenient synthetic methodology for the cyclocondensative transformation of various alkylsulfanylphenylamines with bromoacetyl bromide by supporting on KF-alumina in ionic liquids [bmim][Br] and [bmim][BF4] has been developed to obtain 3-oxo-1,4-benzothiazine in good yields. The product is easily obtained by extraction with ethyl acetate and concentrating under vacuum. Easy recovery of ionic liquid and use in consecutive reactions is also reported.
Published online: 5th March, 2004
■ Facile Synthesis of 4H-1,3-Benzoselenazines by the Aryne Reaction
U. Narasimha Rao, Ramadas Sathunuru, and Edward R. Biehl*
*Chemistry Department, Southern Methodist University, Dallas, TX 75275-0314, U.S.A.
Abstract
Attempts to prepare benzoselenazoles by trapping benzynes with selenoureas failed. These reactions gave instead symmetrically substituted diaryl diselenides. However, when the selenoureas were converted to selenoazadienes, 4H-1,3-benzoselenazines were obtained in excellent yields. Furthermore, addition of the selenium atom of the selenoazadienes occurred regioselectively at the position 1 of 3-methoxybenzyne and 3,4-dimethoxybenzyne.
Published online: 26th March, 2004
■ Organic Reactions in Ionic Liquids: A Simple Highly Regioselective or Regiospecific Substitutions of Benzotriazole
Zhang-Gao Le, Zhen-Chu Chen,* Yi Hu, and Qin-Guo Zheng
*Department of Chemistry, Zhejiang Universityh (XiXi Campus), Hangzhou, Zhejiang 310028, China
Abstract
In the absence of any added base in ionic liquids [Bmim][BF4], benzotriazole replaces the halogen atom of an α-halogenated ketone or α-halogenated carboxylic ester to give the corresponding N-1-substituted benzotriazole as the only isomer, and 1-chloro-2,4-dinitrobenzene reacted similarly with benzotriazole to afford the N-1-substituted benzotriazole in a good yield. Alkyl halides reacted regioselectively to afford the N-1-alkylbenzotriazole in ratios of more than 15 to 1 over the N-2-isomer.
Published online: 5th March, 2004
■ Synthesis of Fluorescent Derivatization Reagents: Reaction of Isatin with 3-Aryl-7-diethylaminocoumarins and Their Fluorescent Properties
Naozumi Nishizono,* Kazuaki Oda, Yutaka Kato, Kosei Ohno, Masaru Minami, and Minoru Machida
*Faculty of Pharmaceutical Sciences, Health Sciences University of Hokkaido, Ishikari-Tobetsu, Hokkaido 061-0293, Japan
Abstract
Fluorescent derivatization reagents, 3-aryl-7-diethylaminocoumarin derivatives, were synthesized and reacted with isatin to give the adduct. Their fluorescent properties are discussed.
Published online: 12th March, 2004
■ Synthesis of Substituted 1,4-Benzoxazepin-3-one Derivatives
Yann Davion, Gérald Guillaumet, Jean-Michel Léger, Christian Jarry, Brigitte Lesur, and Jean-Yves Mérour*
*Instiut de Chimie Organique et Analytique, C.N.R.S., Unviersité d’Orléans, BP 6759, Rue de Chartres, 45067 Orleans Cedex, France
Abstract
A synthesis of substituted 1,4-benzoxazepin-3-one is described starting from salicylaldehyde, aniline and chloroacetyl chloride. Use of 2-bromo-3-phenylpropionyl chloride gave access to 2-benzyl-1,4-benzoxazepin-3-one; an addition/elimination sequence afforded the corresponding benzylidene derivative which structure has been confirmed by an X-Ray analysis. Biphenyl substituents were also introduced in position -4 of this scaffold.
Published online: 26th March, 2004
■ A New Synthetic Route to YM087, an Arginine Vasopressin Antagonist
Takashi Tsunoda,* Akihiro Tanaka, Toshiyasu Mase, and Shuichi Sakamoto
*Yamanouchi Pharmaceutical Co., Ltd., Chemical Technology Labs., Yamanouchi Pharmaceutical Co., Ltd., 160-2, Akahama, Takahagi-shi, Ibaraki, Japan
Abstract
A new synthesis of N-{4-[(2-methyl-4,5-dihydroimidazo[4,5-d][1]benzazepin-6(1H)-yl)carbonyl]phenyl}biphenyl-2-carboxamide monohydrochloride (1, YM087) via new imidazobenzazepine intermediates is described. This method remarkably improves the overall yield of 1 compared to the original synthesis providing a more safe, reliable and cost-efficient approach to 1.
Published online: 30th March, 2004
■ Gliocladins A - C and Glioperazine ; Cytotoxic Dioxo- or Trioxopiperazine Metabolites from a Gliocladium Sp. Separated from a Sea Hare
Yoshihide Usami,* Junko Yamaguchi, and Atsushi Numata
*Osaka University of Pharmaceutical Sciences, 4-20-1 Nasahara, Takatsuki, Osaka 569-1094, Japan
Abstract
New dioxo- or trioxopiperazine metabolites named gliocladins A-C (1 - 3) and glioperazine (4) have been isolated from a strain of Gliocladium sp., originally separated from the sea hare. Their structures have been elucidated by spectroscopic analyses using various NMR spectroscopic techniques. Structurally unique trioxopiperazine (3) exhibited significant cytotoxicity against cultured P388 cells.
Published online: 26th March, 2004
■ Synthesis of Isotope Labeled Me(3a)-13C-Physostigmine and Debromoflustramine B
Martha S. Morales-Ríos,* Norma F. Santos-Sánchez, Yolanda Mora-Pérez, and Pedro Joseph-Nathan
*Departamento de Química, Centro de Investigación y de Estudios Avanzados, I.P.N, Apartado 14-740, México, D.F., 07000, Mexico
Abstract
A versatile and concise synthetic route for the synthesis of selectively functionalized pyrrolo[2,3-b]indole alkaloid analogues has been developed starting from 3-indolylacetonitriles. Employing this route, physostigmine with 13C-enrichment at Me(3a) (99 atom% 13C) and debromoflustramine B have been prepared.
Published online: 8th March, 2004
■ Pyridazine Derivatives and Related Compounds Part 10. Reactions of 3-Diazopyrazolo[3,4-c]pyridazine with Reactive Methylene Compounds and Other Groups
Ali Deeb* and Mahmoud Kotb
*Department of Chemistry, Faculty of Science, Zagazig University, Zagazig, Egypt
Abstract
3-Diazopyrazolo[3,4-c]pyridazine was synthesized and its transformations were investigated. With reactive methylene compounds the corresponding hydrazones and condensed 1,2,4-triazines were formed. With aromatic amines and naphthols the diazo compound was converted into arylazo derivatives. The diazo compound underwent cycloaddition, reacting as a 1,4-dipole to yield cycloaddition products.
Published online: 5th March, 2004
■ A Convenient Synthesis of Some New 1,3,4-Benzothiadiazepin-5-ones
Jalal A. Zahara, Bassam A. Abu Thaher, Mustafa M. El-Abadelah,* and Roland Boese
*Institut für Anorganische Chemie, Universität Duisburg-Essen, Campus Essen, Universitätstrasse, 3-5, D-45117 Essen, Germany
Abstract
A synthesis of new 1,3,4-benzothiadiazepin-5-ones (6a-c) has been achieved via cyclocondensation, promoted by acetic anhydride at reflux, of the corresponding acyclic 2-{[2-oxo-1-(N-arylhydrazono)propan-1-yl]mercapto}benzoic acids (4a-c). Structural assignments of the heterocyclic products (6a-c) are based on analytical, spectral (IR, MS and NMR) and X-Ray crystal structure data.
Published online: 24th February, 2004
■ A Solvent-free Method for Substituted Imidazolidin-4-ones Synthesis
Jirí Pospísil and Milan Potácek*
*Department of Organic Chemistry, Faculty of Science, Masaryk University, Kotlárská 2, CZ-61137 Brno, Czech Republic
Abstract
A new method of the solvent-free synthesis of substituted imidazolidin-4-ones is described. The method is developed for microwave-assisted solvent-free conditions and compared with classical thermally initiated solvent-free conditions. In both cases the reaction proceeds with good yields. However, the reaction under microwave conditions is accelerated six-times. Thermal effect of the microwaves is observed.
Published online: 19th March, 2004
■ Synthesis of 1,2,3-Triazoles
Dolly, Belen Batanero, and Fructuoso Barba*
*Departments of Organic and Inorganic Chemistry, University of Alcalá, 28871 Alcalá de Henares (Madrid), Spain
Abstract
4-Phenyl-1-(p-toluenesulfonamido)-1,2,3-triazole (1) is obtained when phenacyl halides react with tosyl hydrazide in one-pot process.
Published online: 24th February, 2004
■ A New Diterpene Alkaloid from Aconitum brunneum Hand-Mazz
Liming Gao, Xiaomei Wei, Xiaoling Jin, and Li Yang*
*National Laboratory of Applied Organic Chemistry, Department of Chemistry, Lanzhou University, Lanzhou 730000, China
Abstract
A new diterpenoid alkaloid, 3α-hydroxy-12-epi-napelline (1), was isolated from the ethanol extract of the roots of Aconitum brunneum Hand-Mazz along with six known alkaloinds, i.e., 12-epi-napelline (2), liangshanine (3), 12-epi-dehydronapelline (4), songorine (5), aconitine (6) and benzoylaconine (7). The structure of the new compound was elucidated by spectroscopic methods.
Published online: 12th March, 2004
■ Synthesis of New Medium Ring Aromatic Lactones via Halocyclization of 2-Hydroxyphenylalkanoic Acid Allylic Esters
David P. Brown* and Lalitha Krishnamurthy
*Department of Chemistry, St. John’s University, 8000 Utopia Parkway, Jamaica, New York 11439, U.S.A.
Abstract
Stable medium size ring aromatic lactones have been synthesized through electrophilic heteroatom cyclization reactions in moderate yields.
Published online: 16th February, 2004
■ Synthesis of Heterocyclic Compounds from the Reactions of Dehydroacetic Acid (DHA) and Its Derivatives
Om Prakash,* Ajay Kumar, and Shiv P. Singh
*Department of Chemistry, Kurukshetra University, Kurukshetra, Haryana, 136119, India
Abstract
3-Acetyl-4-hydroxy-6-methyl-2-oxo-2H-pyran (Dehydroacetic acid, DHA) and its simple derivatives such as 3-cinnamoyl-4-hydroxy-6-methyl-2-oxo-2H-pyrans (Chalcone analogues of DHA) find interesting applications in the synthesis of various heterocyclic compounds. The review highlighting this aspect covers literature up to 2003.