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. 12, 2004
Published online: 19th October, 2004
■ Isolation and Identification of Phototropism-regulating Substances Benzoxazinoids from Maize Coleoptiles
Tsuyoshi Hasegawa, Kosumi Yamada,* Hideyuki Shigemori, Kensuke Miyamoto, Junichi Ueda, and Koji Hasegawa
*Graduate School of Life and Environmental Sciences, University of Tsukuba, Tsukuba, Ibaraki 305, Japan
Abstract
As candidate(s) for phototropism-regulating substance(s), three substances were isolated from blue light-illuminated maize coleoptiles and identified as 2-O-β-D-glucopyranosyl-4-hydroxy-7-methoxy-(2H)-1,4-benzoxazin-3(4H)-one (DIMBOA glucoside), 2,4-dihydroxy-7-methoxy-(2H)-l,4-benzoxazin-3(4H)-one (DIMBOA) and 6-methoxy-2-benzoxazolinone (MBOA) from their 1H NMR spectra. Phototropic stimulation rapidly decreased the inactive DIMBOA glucoside, and abruptly increased the most active DIMBOA and then the active MBOA in the illuminated halves of maize coleoptiles. These results suggest that DIMBOA plays the essential role in the phototropism of maize coleoptiles.
Published online: 26th October, 2004
■ Selective Recognition of Rotaxanes for an Alkali Metal Ion
Yuji Tokunaga,* Suzuka Kakuchi, and Youji Shimomura
*Department of Materials Science and Engineering, Faculty of Engineering, Fukui University, Bunkyo, Fukui 910-8507, Japan
Abstract
Rotaxanes possessing a crown ether as a wheel group and oligo ethylene glycol units in the dumbbell group were synthesized using hydrogen bonding guided self-assembly and diphenyldiazomethane ester forming end-capping of pseudorotaxanes. The selective recognition of the lariat-crown-like rotaxanes for lithium ion was discovered. That recognition depended on the number of ethylene glycol units.
Published online: 26th October, 2004
■ Rapid Access to Glucopyranosyl-1,2,3-triazoles via Cu(I)-Catalyzed Reactions in Water
Rakesh A. Akula, David P. Temelkoff, Nicole D. Artis, and Peter Norris*
*Department of Chemistry, Youngstown State University, 1 University Plaza, Youngstown, OH 44555-3663, U.S.A.
Abstract
1-Azido-1-deoxy-2,3,4,6-tetra-O-acetyl-β-D-glucopyranose reacts with various terminal alkynes in the presence of CuSO4/ascorbic acid in water to give the corresponding 1,4-disubstituted 1,2,3-triazoles, which are isolated in high yield and purity by simply filtering the precipitate from the reaction mixture. Several sugar-derived acetylenes react similarly to yield triazole-linked disaccharide analogs.
Published online: 8th October, 2004
■ Synthesis of New Potential HIV-1 Integrase Inhibitors
Stefania Ferro, Angela Rao, Maria Zappalà, Alba Chimirri, Maria Letizia Barreca, Myriam Witvrouw, Zeger Debyser, and Pietro Monforte*
*Dipartimento Farmaco-Chimico, Università di Messina, Viale Annunziata, 98168 Messina, Italy
Abstract
A synthesis of some 1,2-(hetero)arylsubstituted ethanone and 1,3-(hetero)arylsubstituted 3-hydroxypropenone derivatives, designed as potential HIV-1 integrase inhibitors, is reported. The microwave-assisted synthesis was applied in several reactions achieving reductions in reaction times and high yields. All compounds prepared were tested to explore their potential anti-HIV activity.
Published online: 8th October, 2004
■ Useful Synthesis of 2,3,6-Tri- and 2,3,5,6-Tetrasubstituted Pyridine Derivatives from Aspartic Acid
Yasuchika Yonezawa, Akihito Konn, and Chung-gi Shin*
*Departmnet of Applied Chemistry, Faculty of Engineering, Kanagawa University, 3-27-1 Rokkakubashi, Kanagawa-ku, Yokohama 221-8686, Japan
Abstract
New synthetic methods for 2,3,6-tri- and 2,3,5,6-tetrasubstituted pyridine skeletons, which are the essential main central segments of thiostrepton-type macrocyclic antibiotics, were developed from L-α-aspartic acid (Asp) via the Asp-derived α-dehydroamino acid ester.
Published online: 26th October, 2004
■ Stereoselective Synthesis of 1-Substituted 1,2,3,4-Tetrahydro-β-carbolines by Asymmetric Electrophilic α-Amidoalkylation Reactions
Ulrich Weber, Cornelia Hoesl, W. Ponikwar, M. Suter, Heinrich Nöth, and Klaus T. Wanner*
*Department of Pharmacy, Ludwig-Maximilians-University of Munich, Butenandtstr. 5-13 Haus C, D-81377 Munich, Germany
Abstract
An efficient procedure for the asymmetric synthesis of 1-substituted 1,2,3,4-tetrahydro-9-methyl-β-carbolines based on asymmetric electrophilic α-amidoalkylation reactions is described. Stereoselective addition of various organometallic reagents to a chiral N-acyl-β-carbolinium ion gave the corresponding 1-substituted 1,2-dihydro-β-carbolines in high yields and very good to excellent diastereomeric ratios. Catalytic hydrogenation followed by the removal of the chiral auxiliary via reductive cleavage of the amide bond proceeded with complete conservation of the absolute configuration at the newly created stereocenter leading to 1-substituted 1,2,3,4-tetrahydro-9-methyl-β-carboline derivatives in high yields. Their absolute stereochemistry was proven by X-Ray analysis. The 1-phenyl-substituted 1,2,3,4-tetrahydro-β-carbolines were evaluated for their affinity to the PCP binding site of the NMDA receptor.
Published online: 22nd October, 2004
■ Synthesis of 2-Arylbenzothiazoles and Imidazoles Using Scandium Triflate as a Catalyst for Both a Ring Closing and an Oxidation Steps
Takashi Itoh, Kazuhiro Nagata, Hiroyuki Ishikawa, and Akio Ohsawa*
*School of Pharmaceutical Sciences, Showa University, 1-5-8 Hatanodai, Shinagawa-ku, Tokyo 142-8555, Japan
Abstract
2-Aminobenzenethiol and an aryl aldehyde were allowed to react to give a 2-arylbenzothiazole in good yield in the presence of a catalytic amount of scandium triflate Sc(OTf)3. The detailed study showed that Sc(OTf)3 catalyzed two steps, that is, the formation of a thiazoline ring and the oxidation of the thiazoline to a thiazole ring. This is the first example that scandium(III) ion catalyzed oxidation of an organic compound using molecular oxygen as an oxidant. The reaction was applied to o-phenylenediamine and an aryl aldehyde to give corresponding 2-arylbenzimidazole in moderate to good yields depending upon the structure of aldehyde.
Published online: 8th October, 2004
■ Preparation of Benzothiopyrano[2,3-b]indoles by the Reaction of 1,3-Dihydroindole-2-thiones with Certain Dienophiles
Sukanta Kamila and Ed Biehl*
*Chemistry Department, Southern Methodist University, Dallas, TX 75275-0314, U.S.A.
Abstract
Benzothiopyrano[2,3-b]indoles were prepared by the cyclization of 1,3-dihydroindole-2-thiones with various dienophiles. The 1,3-dihydroindole-2-thiones were readily synthesized by the reaction of oxindole with P2S5 followed by a piperidine-mediated condensation of the resulting thioindole with a suitable aromatic aldehyde.
Published online: 26th October, 2004
■ Synthesis of 1,4:3,6-Dianhydro-D-mannitol 2,5-(Hydrogen Phosphate) and Its Usage in Palladium-catalyzed Hydroxycarbonylation of Styrene
Biao Jiang,* Zuo-Gang Huang, and Ke-Jun Cheng
*State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, 354 Finglin Road, Shanghai 200032, China
Abstract
Phosphorylation of 1,4:3,6-dianhydro-D-mannitol by phosphorus oxychloride in the presence of triethylamine followed by hydrolysis gave a cyclic hydrogen phosphate, which has the crystal structure of 6-hydroxy-6-oxo-2,5,7,10- tetraoxa-6-phospha-tricyclo[6.3.0.04,11]undecane. It was used as a chiral ligand in palladium-catalyzed hydroxycarbonylation of styrene. The regioselectivity was good, but the optical yield was limited.
Published online: 26th October, 2004
■ Facile Synthesis of 5-Acyl-2-amino-1,3-thiazole by the Reaction of Thiaazadienes with α-Haloketones
Ramadas Sathunuru and Ed Biehl*
*Chemistry Department, Southern Methodist University, Dallas, TX 75275-0314, U.S.A.
Abstract
The reaction of thiaazadienes (1a–e) with α-halo ketones (2a–d) gives 5-acyl-2-amino-1,3-thiazole (3a–q) in high yields.
Published online: 26th October, 2004
■ A New Method for the Preparation of Nitrogen-containing Heterocycles Using Diphenylsulfonium Triflates
Hiroyuki Yamanaka, Yoshinobu Yamane, and Teruaki Mukaiyama*
*Center for Basic Research, The Kitasato Institute, 6-15-5 (TCI), Toshima, Kita-ku, Tokyo 114-0003, Japan
Abstract
Various nitrogen heterocycles were produced by the reactions of ω-bromoalkyldiphenylsulfonium or diphenylvinylsulfonium triflates with nitrogen nucleophiles. Further, the reactions of diphenylstyrylsulfonium triflates with N-metalated phthalimide and imidazoles afforded α-phthalimidostyrenes and α-(imidazol-1-yl)styrenes in good yields, respectively.
Published online: 8th October, 2004
■ Organopalladium Complex Containing 5-Amino-3H-1,3,4-thiadiazolin-2-ones as Metalloreceptor for DNA/RNA Nucleobases
Nam Sook Cho,* Chun Ho Lee, Yeong-Joon Kim, Jae Soo Choi, and Sung Kwon Kang
*Department of Chemistry, College of Natural Sciences, Chungnam National University, Taejon 305-764, Korea
Abstract
Macrocycles containing two 5-amino-3H-1,3,4-thiadiazolin-2-ones linking the 3- and 5-positions of the heterocycle unit and one 1,3-benzenedimethanethiol were prepared via the regiospecific N-alkylation of 5-amino-3H-1,3,4-thiadiazolin-2-one. The 1,3-benzenedimethanethiol sites chelated to palladium metal ion to give an organopalladium metalloreceptor. The structures of the macrocycle and metalloreceptor were established using 1H and 13C NMR, IR, and MS spectrometry. The molecular recognition of the metalloreceptor (5) was examined for some DNA/RNA nucleobases using 1H NMR spectrometry. The complexation ability increased in the order uracil/thymine < adenine < cytosine/imidazole.
Published online: 26th October, 2004
■ Two New Bicoumarins from the Leaves of Murraya exotica
Naoko Teshima, Mayumi Tsugawa, Akiko Tateishi, Mariko Tokumaru, Rie Matsubara, Tetsutaro Kimachi, Motoharu Ju-ichi,* Chihiro Ito, and Hiroshi Furukawa
*Faculty of Pharmaceutical Sciences, Mukogawa Women’s University, 11-68 Koushien Kyuban-Cho, Nishinomiya, Hyogo 663-8179, Japan
Abstract
Two new bicoumarins, named murradimerin A (1) and murramarin B (5) were isolated from the leaves of Murraya exotica (Rutaceae) collected in Ishigaki-island Japan. Their structures were elucidated on the basis of spectroscopic data especially using 2D NMR spectrum. Naturally occurring bicoumarin connected two coumarin moieties by orthoester structure as in murramarin (5) is unusual type and murramarin B (5) is the first example not possessing furanocoumarin moiety.
Published online: 8th October, 2004
■ Synthesis of N1-Demethyl-20-deethylsuaveoline, the Structure Proposed for Sellowiine
Masashi Ohba* and Itaru Natsutani
*Advanced Science Research Center, Kanazawa University, Kakuma, Kanazawa, Ishikawa 920-1192, Japan
Abstract
A synthesis of Na-demethyl-20-deethylsuaveoline (1), the structure assigned to the Rauwolfia alkaloid sellowiine, has been accomplished for the first time through a route using intramolecular oxazole–olefin Diels–Alder reaction. The 1H- and 13C-NMR spectral data and the specific rotation of the synthetic 1 were in disagreement with those reported for a natural sample, leaving the chemistry of this alkaloid incomplete.
Published online: 26th October, 2004
■ Thiazolidinone-annulated Pyrrolobenzodiazepines. Syntheses and Properties of a New Ring System
Andreas Schmidt,* Abbas Gholipour Shilabin, and Martin Nieger
*Institute of Organic Chemistry, Technical University of Clausthal, Leibnizstrasse 6, D-38678 Clausthal-Zellerfeld, Germany
Abstract
New derivatives of pyrrolo[2,1-c][1,4]benzodiazepines were synthesized starting from a thiolactam and 2-bromoacetyl chlorides. Spectroscopic investigations and an X-Ray analysis are presented.
Published online: 29th October, 2004
■ Palladium(II)-mediated Nucleophilic Cyanation of 4-Substituted Quinoline 1-Oxide in the Presence of Trimethylsilyl Cyanide and an Oxidant
Yoshinobu Tagawa,* Yoshitaka Higuchi, Kenji Yamagata, Kazuhiko Shibata, and Daisuke Teshima
*Faculty of Pharmaceutical Sciences, Fukuoka University, Nanakuma, Jonan-ku, Fukuoka, 814-0180, Japan
Abstract
Reaction of 4-substituted (electron-releasing group) quinoline 1-oxides (1) with trimethylsilyl cyanide in the presence of palladium(II) acetate and DDQ gave 2-cyano-4-substituted quinoline 1-oxides (2) in THF in moderate yields. It was reasoned that this reaction proceeds through palladium-catalyzed dehydrosilylation.
Published online: 29th October, 2004
■ Electrophilic Reaction of N-Lewis Acid and N-Oxide Lewis Acid Complexes of 4-Methylpyridines and Their N-Oxides through Base-induced Deprotonation
Yoshinobu Tagawa,* Manami Nomura, Kenji Yamagata, Daisuke Teshima, Kazuhiko Shibata, and Yohinobu Goto
*Faculty of Pharmaceutical Sciences, Fukuoka University, Nanakuma, Jonan-ku, Fukuoka, 814-0180, Japan
Abstract
The comparative studies were carried out on the relative reactivity of 4-methylpyridines, their N-oxides and their Lewis acid complexes towards electrophilic reaction. α-Deprotonation in pyridine ring rather than deprotonation of active methyl group or metal-halogen exchange occurred preferentially in the reaction of N- and N-oxides BF3 complexes with electrophile in the presence of LTMP-TMEDA in THF to give α-substituted-4-methylpyridines and their N-oxides.
Published online: 26th October, 2004
■ Synthesis and Absorption Properties of Zinc-Phthalocyanines with Photoresponsive Azobenzene Groups
Ki-Jong Han and Kwang-Yol Kay*
*Department of Molecular Science and Technology, Ajou University, Suwon 442-749, Korea
Abstract
The phthalocyanines (1) and (2) with eight photoisomerizable azobenzene groups have been synthesized and spectroscopically characterized. These macrocycles exhibit partial trans-cis isomerzation properties upon irradiation of UV/VIS light.
Published online: 8th October, 2004
■ Heterocycles Directly Linked to 3-Position of 1-Benzopyran-4-ones
Chandra Kanta Ghosh
*Department of Biochemistry, University of Calcutta, Kolkata 700019, India
Abstract
Syntheses and some important reactions of the title systems are reviewed.