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. 75, No. 4, 2008
Published online: 26th November, 2007
■ Organocatalytic Asymmetric Synthesis Using Proline and Related Molecules. Part 2.
Hiyoshizo Kotsuki,* Hideaki Ikishima, and Atsushi Okuyama
*Laboratory of Natural Product Chemistry, Faculty of Science, Kochi University, Akebono-cho, Kochi 780-8520, Japan
Abstract
Organocatalytic asymmetric synthesis has been extensively studied and several important procedures for preparing optically active organic compounds have been developed. Research activities in this area have progressed rapidly in the last ten years. This review addresses the most significant advances in asymmetric synthesis using proline and related chiral organocatalysts, mainly from the viewpoint of synthetic applications. This includes (1) Mannich reactions, (2) Michael addition reactions, (3) α-oxidation, (4) α-amination, (5) α-sulfenylation / selenenylation, (6) α-halogenation, (7) cycloaddition reactions, and (8) miscellaneous reactions such as C-C bond formation, epoxidation / oxidation, and reduction.
Published online: 28th December, 2007
■ Scope and Limitations of the T-Reaction Employing Some Functionalized C-H-Acids and Naturally Occurring Secondary Amines
Constantin Rabong, Christian Hametner, Kurt Mereiter, Victor G. Kartsev, and Ulrich Jordis*
*Institute of Applied Synthetic Chemistry, Vienna University of Technology, Getreidemarkt 9/163, 1060 Vienna, Austria
Abstract
Scope and limitations of the T-reaction with emphasis on using chiral, natural products as starting materials to prepare novel chiral heterocycles is studied and the diastereoselective introduction of newly formed stereocenters is explained via proposed mechanisms.
Published online: 11th January, 2008
■ The Reaction of Hexachlorocyclotriphosphazatriene with Bromoneopentyl Glycol
Hanife Ibisoglu,* Ferda Hacivelioglu, and Adem Kiliç
*Department of Chemistry, Gebze Institute of Technology, Gebze 41400, Kocaeli, Turkey
Abstract
In the present work, novel phosphazene derivatives, monospiro- (1), dispiro- (2), and trispiro-2,2-bis(bromomethyl)-1,3-propandioxy (3) substituted cyclotriphosphazatrienes were synthesized with the reaction of bromoneopentyl glycol(2,2-bis(bromomethyl)-1,3-propandiol) with hexachlorocyclotriphosphazatriene, N3P3Cl6. The structures of the compounds were determined by elemental analysis, mass spectrometry, 1H and 31P NMR spectroscopy. The thermal properties of the compounds (1), (2) and (3) were investigated by DSC and TGA.
Published online: 11th January, 2008
■ Synthesis of Nitrogen-Containing Heterocycles 11. 1,2,4-Triazole Formation through Disproportionation of Polyazapolyenes
Yoshiko Miyamoto
*Department of Chemistry, Kitasato University of Japan, 1-15-1 Kitasato, Sagamihara, Kanagawa 228-8555 Japan
Abstract
Aromatic diaminomethylenehydrazones 1-4 were reacted with bis(methylthio)methylenemalononitrile (BMM) to give 5-aryl-1-benzyl-3-dimethylamino-1H-1,2,4-triazoles (5-8) via disproportionation in fused condition in moderate to high yields (44-78 %). Little or no effect was observed on disproportionation products in connection with substituents on the benzene ring. When used an equimolar amount of two different diaminomethylenehydrazones 3 and 4, four types of 5-aryl-1-benzyl-3-dimethylamino-1H-1,2,4-triazoles were obtained. In the reaction using two (different) benzaldehyde S-methylisothiosemicarbazones 22 and 23, four types of 5-aryl-1-benzyl-3- methylthio-1H-1,2,4-triazoles were formed in 14-26 % yield. The structural assignment of products and reaction mechanism are discussed.
Published online: 18th December, 2007
■ Synthesis of 6-Aminoalkyldiquino-1,4-thiazines and Their Acyl and Sulfonyl Derivatives
Malgorzata Jelen and Krystian Pluta*
*Department of Organic Chemistry, The Medical University of Silesia, Jagielloñska 4, 41-200 Sosnowiec, Poland
Abstract
Syntheses of various 6-dialkylaminoalkyldiquino-1,4-thiazines (5-8) and 6-aminoalkyldiquino-1,4-thiazines (11-13) were elaborated in the reactions of diquino-1,4-dithiin (2) and 2,2’-dichloro-3,3’-diquinolinyl sulfide (3) with primary amines, and 6H-diquino-1,4-thiazine (4) with dialkylaminoalkyl chlorides and phthalimidoalkyl bromides followed by hydrolysis. 6-Aminoalkyldiquinothiazines (11-13) were transformed into acyl and sulfonyl derivatives (15-26). Some of the obtained compounds showed significant anticancer activity.
Published online: 18th January, 2008
■ Synthesis and Properties of 3,3’-Polymethylene-2,2’-bibenzo[b]-1,10-phenanthrolines
A. F. M. Motiur Rahman and Yurngdong Jahng*
*College of Pharmacy, Yeungnam University, Gyeongsan 712-749, Korea
Abstract
The Friedländer reactions of 4-aminoacridine-3-carbaldehyde with cyclcoalkane-1,2-diones were examined. The reactions of cycloheptane- and cycloocatane-1,2-diones afforded 3,3’-tri- and 3,3’-tetramethylene-2-(pyrid-2’-yl)benzo[b]-1,10-phenanthrolines in 20% and 80%, respectively, while reactions with butane-2,3-dione, cyclopentane-1,2-dione and cyclohexane-1,2-dione afforded only unexpected benzo[b]-1,10-phenanthroline. The trimethylene-bridge is flexible at room temperature while the tetramethylene units are rigid enough to magnetically differentiate all the 8 aliphatic protons at room temperature in NMR time scale even though showing two aliphatic carbon resonaces as expected.
Published online: 11th January, 2008
■ Synthesis and Evaluation of Influenza Virus Sialidase Inhibitory Activity of Hinokiflavone-Sialic Acid Conjugates
Kazuhiko Miki, Takayuki Nagai, Takayuki Nakamura, Mitsuru Tuji, Kiyotaka Koyama, Kaoru Kinoshita, Kimio Furuhata, Haruki Yamada, and Kunio Takahashi*
*Department of Pharmacognosy and Phytochemistry, Meiji Pharmaceutical University, Noshio 2-522-1, Kiyose-shi, Tokyo 204-8588, Japan
Abstract
The known biflavonoid, hinokiflavone (1) was isolated from the leaves of Metasequoia glyptostroboides Hu et Cheng and displayed influenza A and B virus sialidase inhibitory activity. The unnatural glycoconjugate, hinokiflavone-sialic acid (8) was synthesized and exhibited more potent inhibitory activity.
Published online: 11th January, 2008
■ Synthesis and Antimicrobial Evaluation of Some New Pyrimidine Derivatives
Nabila A. Kheder, Yahia N. Mabkhot, and Ahmad M. Farag*
*Department of Chemistry, Faculty of Science, Cairo University, Giza 12613, Egypt
Abstract
The utility of ethyl 6-methyl-2-oxo-4-phenyl-1,2-dihydropyrimidine- 5-carboxylate (1) in the synthesis of some new pyrido[1,2-f]pyrimidine, pyrazolo[3,4-b]pyrido[1,2-f]pyrimidine, 6-(4-substituted styryl)pyrimidine, pyrido[4,3-d]pyrimidine, pyrimido[5,4-d]pyridazine and substituted-6-(thien-2-yl)pyrimidine derivatives is reported. Antimicrobial evaluation of some selected examples from the synthesized products was carried out.
Published online: 18th December, 2007
■ Transformation of 1,5-Diphenylpentane-1,3,5-trione. The Synthesis of Substituted (4H)-Pyranones, Pyridin-4(1H)-ones and 4H-Pyrano[3,2-c]pyridin-4-ones
Silvo Zupancic, Jurij Svete, and Branko Stanovnik*
*Faculty of Chemistry and Chemical Technology, University of Ljubljana, Askerceva 5, P. O. Box 537, 1000 Ljubljana, Slovenia
Abstract
1,5-Diphenylpentane-1,3,5-trione (1) was transformed by the reaction either with N,N-dimethylformamide dimethylacetal (DMFDMA) or N,N-dimethylacetamide dimethylacetal (DMADMA) into (N,N-dimethylamino)- methylidene derivatives 2a,b as intermediates. They were converted in the presence of silica gel into 5-benzoyl-2-phenylpyran-4-one (3a) and its 6-methyl derivative 3b, while the corresponding 5-benzoyl- 2-phenylpyridin-4(1H)-one (4) was formed by the reaction with NH4Cl. Compound 3b gave the corresponding (N,N-dimethylamino)methylidene derivative 5 with DMFDMA, which was cyclized in aqueous ammonia into 2,5-diphenyl-4H-pyrano[3,2-c]pyridin-4-one (7). The reaction of 1 with excess of DMFDMA followed by reaction with ammonia or primary amines yielded 1-substituted 3,5-dibenzoylpyridin-4(1H)- ones (9a-m).
Published online: 28th December, 2007
■ Two New Taxoids from the Needles and Young Stems of Taxus cuspidata
Liyan Wang,* Liming Bai, Daisuke Tokunaga, Yuusuke Watanabe, Jun-ichi Sakai, Wanxia Tang, Yuhua Bai, Katsutoshi Hirose, and Masayoshi Ando*
*Graduate School of Science and Technology, Niigata University, 2-8050 Ikarashi, Nishi-ku, Niigata, 950-2181, Japan
Abstract
A new basic taxoid, taxine NA-13 (1) and a new neutral taxoid, 3α,11α-cyclotaxinine NN-2 (2) were isolated from Japanese yew tree, Taxus cuspidata. The structures of two new taxoids 1 and 2 were established as shown in structure 1 and structure 2 by spectroscopic analysis.
Published online: 18th December, 2007
■ One-Pot Synthesis of 2,3-Disubstituted Benzo[b]thiophene Derivatives from 2-Mercaptophenyl Ketones
Kazuhiro Kobayashi,* Daizo Nakamura, Shuhei Fukamachi, and Hisatoshi Konishi
*Department of Materials Science, Faculty of Engineering, Tottori University, 4-101 Koyama-minami, Tottori 680-8552, Japan
Abstract
2-Mercaptophenyl ketones have been found to react with activated alkyl bromides (BrCH2EWG’s), such as bromoacetates, bromoacetonitrile, and bromomethyl phenyl ketone, in the presence of two molar amounts of sodium hydride in THF at 0 °C to afford 2,3-disubstituted benzo[b]thiophenes in generally good to excellent yields.
Published online: 18th December, 2007
■ Rapid Synthesis of New Azaheterocyclic Hydroxymalonate Derivatives Using TDAE Approach
Marc Montana, Maxime D. Crozet, Caroline Castera-Ducros, Thierry Terme, and Patrice Vanelle*
*Laboratory of Pharmaceutical Organic Chemistry, CNRS-UMR 6517, University of Méditerranée, Faculty of Pharmacy, 27 bd Jean Moulin, 13385 Marseille cedex 5, France
Abstract
A new series of azaheterocyclic hydroxymalonate derivatives was synthesized from reaction between chloromethyl azaheterocycles and diethyl oxomalonate using tetrakis(dimethylamino)ethylene (TDAE).
Published online: 18th January, 2008
■ Calamistrins H and I, Two Linear Annonaceous Acetogenins from the Roots of Uvaria calamistrata Hance
Guang-Xiong Zhou,* Yanjun Zhang, Ruo-Yun Chen, and De-Quan Yu
*College of Pharmacy, Jinan University, Guangzhou 510632, China
Abstract
Two linear Annonaceous acetogenins, calamistrins H and I (1 and 2) were isolated from an ethanolic extract of the roots of Uvaria calamistrata Hance (Annonaceae) with silica gel column and preparative HPLC. Compounds 1 and 2 belong to a class of acetogenins without tetrahydrofuran (THF) ring on the chain. The structures of 1 and 2 were determined by spectroscopic analysis (NMR and MS) and chemical derivatives.
Published online: 11th January, 2008
■ New Biflavonoids from Cephalotaxus harringtonia var. fastigiata (Cephalotaxaceae)
Hiroaki Sasaki, Kazuhiko Miki, Kiyotaka Koyama, Kaoru Kinoshita, and Kunio Takahashi*
*Department of Pharmacognosy and Phytochemistry, Meiji Pharmaceutical University, Noshio 2-522-1, Kiyose-shi, Tokyo 204-8588, Japan
Abstract
Three new biflavonoids 1 (2,3-dihydro-6-methylginkgetin), 2 (2,3-dihydro-6-methylbilobetin) and 3 (2,3-dihydro-6-methylsequoiaflavone) have been isolated from the leaves of Cephalotaxus harringtonia K. Koch var. fastigiata Rehder (Cephalotaxaceae) and their structures were elucidated by spectral analysis.
Published online: 11th January, 2008
■ Green Protocol for the Friedländer Synthesis: KAl(SO4)2·12H2O-SiO2 (Alum- SiO2), a Highly Efficient Catalyst in the Synthesis of Quinolines
Ali A. Mohammadi,* Javad Azizian, Armin Hadadzahmatkesh, and Mohammad R. Asghariganjeh
*Department of Chemistry, Faculty of Science, Shahid Beheshti University, P. O. Box 19395-4716, Tehran, Iran
Abstract
In this letter, an efficient synthesis of an array of poly-substituted quinolines from 2-aminoaryl ketones and β-ketoester, β-diketones and α-methylene ketones using KAl(SO4)2·12H2O-SiO2 (Alum-SiO2) under solvent-free conditions is described. Compared with the classical Friedländer synthesis this new synthetic method has the advantage of excellent yields (90-98%), shorter reaction time, and reusability of the catalyst.
Published online: 11th January, 2008
■ Synthesis and Reactions of Some New Spiro {Indeno[1,2-b]pyran-4,3’-indolines}
Maher F. El-Zohry,* Yasser A. Elossaily, Thanaa A. Mohamed, and Essam M. Hussein
*Department of Chemistry, Faculty of Science, Assiut University, Assiut 71516, Egypt
Abstract
Indan-1,3-dione (1) reacted with 3-dicyanomethylidene-2-oxoindolines (2a-c) in refluxed ethanol to afford 2-amino-3-cyanospiro{5H-indeno[1,2-b] pyrane-4,3’-(1’-substitutedindoline)}-2’,5-diones (3a-c) which underwent different reactions to afford new spiro{indeno[2’,1’:5,6] pyrano[2,3-d]pyrimidine-5,3’-(1’-substitutedindoline)} (4a,b)-(12a,b) which are analogues of some reported biologically active spiropolycyclic compounds.