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. 55, No. 7, 2001
Published online:
■ An Interrupted Pummerer Reaction Induced by Hypervalent Iodine(III) Reagent: Facile Synthesis of 2-Aryl-1,2-benzisothiazol-3(2H)-ones
Huey-Min Wang, Hsin-Yu Huang, Iou-Jiun Kang, and Ling-Ching Chen*
*Graduate Institute of Pharmaceutical Sciences , Kaohsiung Medical University, 100 Shih Chen 1st Rd., Kaohsiung 80708, Taiwan, R.O.C.
Abstract
Treatment of N-aryl-2-(benzylthio)benzamides with phenyliodine(III) bis(trifluoroacetate) containing trifluoroacetic acid resulted in an interrupted Pummerer-type reaction to give 2-aryl-1,2-benzisothiazol-3(2H)-ones rather than the normal Pummerer-type products.
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■ Synthesis of 1-Hydroxyyohimbine and Its Novel Skeletal Rearrangement Reaction into Oxindole Derivatives
Masanori Somei,* Koichi Noguchi, and Fumio Yamada
*Faculty of Pharmaceutical Sciences, Kanazawa University, 13-1 Takara-machi, Kanazawa 920-0934, Japan
Abstract
1-Hydroxyyohimbine was prepared for the first time. Its skeletal rearrangement reaction either directly into 2-oxindole or into 3-oxindole derivatives by a series of reaction is reported. 1-Hydroxyyohimbine and some of its derivatives showed potent α2 blocking activity.
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■ Acylated Pelargonidin 3-Sophoroside-5-glucosides from the Flowers of the Japanese Morning Glory Cultivar ‘Violet’
Kenjiro Toki, Norio Saito, Shigeru Iida, Atsushi Hoshino, Atsushi Shigihara, and Toshio Honda*
*Faculty of Pharmaceutical Sciences, Hoshi University, 2-4-41 Ebara, Shinagawa-ku, Tokyo 142-8501, Japan
Abstract
Two novel acylated anthocyanins were isolated from the red-purple flowers of Japanese morning glory ‘Violet’ (or ‘Murasaki’) along with three known pigments. These novel pigments were determined to be pelargonidin 3-O-[2-O-(6-O-(trans-cafferyl)-β-D-grucopyranosyl)-β-D-glucopyranoside]-5-O-β-D-glucopyranoside (1), and pelagonidin 3-O-[2-O-(6-O-(trans-p-coumaroyl)-β-D-glucopyranosyl)-β-D-glucopyranoside]-5-O-β-D-glucopyranoside (2). Three known pigments were also identified to be Pharbitis Red anthocyanin 1, and Ipomoea Red anthocyanis 1 and 4.
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■ A New Synthesis of 4-Phenylquinolines by Reaction of 2-(α-Bromobenzyl)oxiranes with Aniline Derivatives
Michinori Karikomi, Hiroshi Tsukada, and Takashi Toda*
*Faculty of Engineering, Utsunomiya University, 7-1-2 Yoto, Utsunomiya 321-8585, Japan
Abstract
Several 4-phenylquinoline derivatives were synthesized by reaction of (2R*,1’R*)-2-(α-bromobenzyl)oxiranes (1a) with aniline derivatives, and the following treatment of the formed 3-hydroxy-4-phenyl-1,2,3,4-tetrahydroquinolines (2) with the Rydon reagent, and potassium t-butoxide and air oxidation.
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■ Stereoselective Synthesis of a Novel Tetracyclic β-Lactam
Do Kyu Pyun, Hee Jung Jung, Hyun Jung Kwak, Jae Hak Kim, Eun Jung Kim, Bong Jin Kim, Moon Hwan Kim, and Cheol Hae Lee*
*Pharmaceutical Division, Korea Research Institute of Chemical Technology, P.O. Box 107, Yusung, Taejon 305-343, Korea
Abstract
Stereocontrolled total synthesis of a novel tetracyclic β-lactam (3) has been achieved in ten steps. The key transformations in this approach are the regioselective ring opening of β-epoxide (5β) and the stereoselective construction of ketoazetidinone (11) from methoxyketo-γ-lactam (9) and 4-acetoxyazetidinone (10).
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■ Inhibition of HIV Integrase by 4-Hydroxycoumarin Dimer Bearing Aniline Mustard Moiety
Pili Chih-Min Mao, Jean-Francois Mouscadet, Herve Leh, Christian Auclair, and Ling-Yih Hsu*
*School of Pharmacy, National Defense Medical Center, P.O. Box 90048-508, Neihu, Taipei, Taiwan, R.O.C.
Abstract
The design, synthesis of novel HIV-integrase (HIV-IN) inhibitors possessing the 4-hydroxycoumarin dimer bearing aniline mustard moiety are described. These compounds showed good inhibitory activity against HIV-IN.
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■ Synthesis of Functionalized 5-Nitrouracil Derivatives Involving Electron Transfer Coupling Reactions
Maxime D. Crozet, Armand Gellis, Mustapha Kaafarani, Michel P. Crozet, and Patrice Vanelle*
*Laboratoire de Chimie Organique, Facultá de Pharmacie, Universitá de la Máditerranáe, 27, Boulevard Jean Moulin, 13385 Marseille Cedex 05, France
Abstract
The tetrabutylammonium salts of 1,3-dialkyl-6-methyl-5-nitrouracils reacted with reductive alkylating agents, p-nitrobenzyl chloride and 2,2-dinitropropane, by electron transfer coupling reactions to yield new potentially active and highly functionalized uracil derivatives.
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■ A Simple Construction of 2-Phenylimino-1,3-thiazolidin-4-ones
Hoh-Gyu Hahn,* Kee Dal Nam, and Heduck Mah
*Organic Chemistry Laboratory, Korea Institute of Science and Technology, P.O. Box 131, Cheongryang, Seoul 136-791, Korea
Abstract
A new methodology for the construction of 2-phenylimino-1,3-thiazolidin-4-one skeleton is described. Reaction of maleic anhydride (5a) or maleimides (5b, 5c) with thiourea (6) gave the corresponding 2-imino-1,3-thiazolidin-4-ones (7) and (9) respectively. The reaction proceeded with high yield in polar solvents. In non-polar solvents at high temperature, however, isothiocyanate (8) was formed as a by-product presumably by the pyrolysis of thiourea (6). The proposed mechanism of the reaction was discussed.
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■ Reaction of 1-Benzenesulfonylindole-2,3-dicarboxylic Anhydride with Wittig Reagents: Synthesis of Pyrrolo[1,2-a]indoles and Cyclopent[b]indole
Yasuyoshi Miki,* Hiroko Hachiken, Atsuko Kawazoe, Yasuhiko Tsuzaki, and Norihide Yanase
*Faculty of Pharmaceutical Sciences, Kinki University, 3-4-1, Kowakae, Higashi-Osaka 577-8502, Japan
Abstract
Treatment of 1-benzenesulfonylindole-2,3-dicarboxylic anhydride with methylenetriphenylphosphorane gave the corresponding ylide. After esterification of the carboxyl group and removal of the benzenesulfonyl group of the ylide, the obtained ylide was reacted with aldehydes to yield α,β-unsaturated ketones, which were converted to pyrrolo[1,2-a]indoles. We also examined the reactivity of the anhydride with (carbethoxymethylene)triphenylphosphorane and (carbethoxyethylidene)triphenylphosphorane.
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■ Synthesis of 5-Deoxy-5-phosphinyl-D-galactopyranose Derivatives: New Phospha-Sugar Analogs of D-Galactose
Tadashi Hanaya,* Ken-ichi Sugiyama, Yasushi Fujii, Akihito Akamatsu, and Hiroshi Yamamoto*
*Department of Chemistry, Faculty of Science, Okayama University, 3-1-1 Tsushima-naka, Okayama 700-8530, Japan
Abstract
The addition reaction of dimethyl phosphonate to 3,6-di-O-benzyl-1,2-O-isopropylidene-α-L-arabino-hexofuranos-5-ulose (11), followed by deoxygenation of 5-hydroxyl group, provided 5-deoxy-5-dimethoxyphosphinyl-D-galactofuranose derivative (13a). Reduction of 13a with sodium dihydrobis(2-methoxyethoxy)aluminate, followed by the action of hydrochloric acid and then hydrogen peroxide, afforded the first D-galactopyranose analog (15) having a phosphinyl group in the hemiacetal ring. This was converted into the 1,2,4-tri-O-acetyl-5-methoxyphosphinyl derivatives (16), whose structure and conformation were established by 1H-NMR spectroscopy.
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■ Efficient Chemoselective Reduction of 3-Substituted Coumarins Utilizing ortho-Phenylenediamine and Benzaldehyde
Francesco Risitano,* Giovanni Grassi, Francesco Foti, and Cristina Bilardo
*Dipartimento di Chimica Organica e Biologica, Università di Messina, Vill. S. Agata, I-98166 Messina, Italy
Abstract
2-Phenylbenzimidazoline, generated in situ from ortho-phenylenediamine and benzaldehyde, is an effective reagent to achieve the chemoselective reduction of the styrenic double bond in 3-substituted coumarins, which takes place in high yield.
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■ A One-Pot Synthesis of Pyrido[2,3-d]- and Quinolino[2,3-d]pyrimidines
Abdel Aziz S. El-Ahl,* Serry A. A. El Bialy, and Mohamed A. Ismail
*Department of Chemistry, Faculty of Science, University of Mansoura, Mansoura, Egypt
Abstract
The in situ formed methylene derivatives of 1,3-dicarbonyl compounds; ethyl cyanoacetate; malononitrile and ketones; react with 6-amino-1,3-dimethyluracil as activated alkenyl derivatives, affording Michael adducts. The adduts simultaneously undergo cyclization to furnish pyrido[2,3-d]- or quinolino[2,3-d]pyrimidine derivatives in high yield.
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■ Convenient New Syntheses of R-(+)-5-Benzyloxymethyl-5H-furan-2-one. A Building Block en route to L-Nucleosides
Fabio Fazio, Davis Maliakal, and Manfred P. Schneider*
*FB-9, Organische Chemie, Bergische Universität - Gesamthochschule Wuppertal, Gaußstraße 20, 42097 Wuppertal, Germany
Abstract
R-(+)-5-Benzyloxymethyl-5H-furan-2-one (R-(1)) was obtained from commercially available R-(-)-2-benzyloxymethyl oxirane (R-(2)) in two and three steps, respectively. Key steps are a) the nucleophilic ring opening of the oxirane moiety with dianions derived from either PhSeCH2CO2H or PhSCH2CO2H; b) oxidation to the corresponding 1-oxides and c) concomitant or thermally induced syn-elimination. R-(1) was obtained with >97% ee and >95% ee, respectively.
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■ Synthesis of Substituted Oxazolo[4,5-b]pyridine Derivatives
Valérie Grumel, Jean-Yves Mérour,* and Gérald Guillaumet
*Institut de Chimie Organique et Analytique, UMR CNRS 6005, BP 6759, Universitá d'Orleans, Rue de Chartres, 45067 Orleans Cedex 2, France
Abstract
Synthesis of new functionnalized oxazolo[4,5-b]pyridines was described. 5-Bromo-3-hydroxy-2-aminopyridine was heated, in the presence of PPSE or PPA, with 4-cyanobenzoic acid, (4-piperidinyl)acetic or propanoic acid to afford 1,3-oxazolo derivatives. Introduction of a carboxylic acid moiety on the pyridine framework was carried out using Heck reaction. The basic moiety, also required for GPIIb/GPIIIa antagonism, was generated by guanylation.
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■ Quinone-cyclized Porfiromycins
Younghwa Na and Harold Kohn*
*Division of Medicinal Chemistry and Natural Products, School of Pharmacy, University of North Carolina, Chapel Hill, North Carolina 27599-7360, U.S.A.
Abstract
Mitomycin C and porfiromycin cyclization has been implicated in the pathway for KW-2149 and BMS-181174 function. The importance of the porfiromycin C(7) structure and nucleophile for quinone cyclization was determined showing that both C(7) and C(8) annulation processes occur.
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■ Review on Reactions of Acetylacetaldehyde with Aromatic and Biogenic Amines and Indoles — Synthesis of Heterocycles via Hydroxymethylene Ketones
Ramiro Quintanilla-Licea* and Hans-Joachim Teuber
*Facultad de Ciencias Químicas, Universidad Autónoma de Nuevo León, Cd. Universitaria, 66400 San NicolÁs, d.l.G., N.L., Mexico
Abstract
In 1960 Teuber et al. started with the study of the reactions of several derivatives of acetylacetaldehyde with aromatic and biogenic amines (dopamine and tryptamine), as well as indole compounds. Teuber’s scientific work resulted in a series of heterocyclic skeletons that are related to alkaloids such as strychnine, yohimbine, ajmalicine and emetine as well as to some analogues of bis-indole alkaloids. We review Teuber’s research results as well as reactions from other authors working in this field obtained within the last 40 years (1960 -2000).