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. 38, No. 7, 1994
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■ Novel Efficient Synthesis and Structural Analysis of Furanose-Type Phosphono Sugars
Mitsuji Yamashita,* Akihiro Yabui, Tatsuo Oshikawa, Tadashi Hanaya, and Hiroshi Yamamoto
*Department of Applied Chemistry, Faculty of Engineering, Shizuoka University, 3-5-1 Johoku, Hamamatsu 432-8561, Shizuoka, Japan
Abstract
Reaction of 2-benzyloxymethyl-1-methoxy-3-phospholene 1-oxide with mCPBA afforded 3,4-epoxyphospholane derivatives, whose isomerized allylic alcohols were cis-dihydroxylated by osmium(VIII) oxide-catalyzed oxidation to give ribo-, arabino-, xylo-, and lyxo-furanose-type phosphono sugars. The nmr data suggest a twist conformation.
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■ Formation of a Strained Triazapentalenoindene Skeleton via the Rearrangement of 2,3-Dihydro-7-nitro-1H-Imidazo[2,1-a]phthalazin-4-ium-6-olate Effected by Dichloroacetic Anhydride
Mónika Fuxreiter, Antal Csámpai,* and János Császár
*Department of Organic Chemistry, Eötvös Loránd University Budapest, H-1518 Budapest 112, P.O.Box 32, Hungary
Abstract
On treatment with dichloroacetic anhydride 2,3-dihydro-7-nitro-1H-imidazo[2,1-a]phthalazin-4-ium-6-olate (5) underwent a backbone rearrangement leading to isoindole derivative (12), which represents a new strained ring system with three condensed five-membered heterocycles. The structure of its stable 3-deacylated form, 3,3a,5a-triaza-1,1-dichloro-1,2,3,3a,4,5,6,6a-octahydro-7-nitropentaleno[3a,3-a]indene-2,6-dione (13) was evidenced by ir, ms, nmr, and X-ray methods.
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■ Addition of Thiols to Acetylene Substituted Indoles
Géza Galambos,* Pál Csókási, Csaba Szántay, Jr., Gábor Gzira, and Csaba Szántay*
*Central Research Institute for Chemistry, Hungarian Academy of Sciences, H-1025 Budapest, P.O.Box 17, Hungary
Abstract
The preparation of synthetically useful thio enol ether substituted indoles is described.
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■ Two Distinct Dynamic Processes in Non-Planar Tetrabenzoporphyrin
Ru-Jen Cheng,* Yu-Ren Chen, and Chun-Chang Chen
*Department of Chemistry, National Chung-Hsing University, Taichung, 402, Taiwan, R.O.C.
Abstract
Two distinct dynamic processes including N-H tautomerism and porphyrin ring inversion have been establised through variable-temperature 1H nmr spectroscopy and isotope effect analysis in meso-tetraphenyltetrabenzoporphyrin consistent with the non-planar nature of the macrocycle from previous structural result.
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■ Pseudothiacrown and Pseudothiolariat Ethers for Double Recognition Systems toward Copper (I) and Silver (I)
Tatsuya Nabeshima,* Ikuo Yosejima, and Yumihiko Yano
*Department of Chemistry, Faculty of Engineering, Gunma University, 1-5-1 Tenjin-cho, Kiryu 376-8515, Japan
Abstract
Linear and branched polythioethers with bipyridine moieties at the termini bind Cu(I) to afford pseudothiacrown and pseudothiolariat ethers by conformational change of the polyether chain, and the pseudocrowns extract Ag(I) selectively.
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■ Diepoxymontin, a Novel Acetogenin from Annona montana
Yang-Chang Wu,* Fang-Rong Chang, Keh-Shaw Chen, Sz-Chi Liang, and Maw-Rong Lee
*Graduate Institute of Natural Products, Kaohsiung Medical College, 100 Shih Chuen 1st Rd., Kaohsiung 80708 Taiwan, R.O.C.
Abstract
Tandem mass spectrometry has been used to elucidate the structure of diepoxide α,β- unsaturated -γ-lactonic acetogenin, diepoxymontin, which is the first example of acetogenin having an adjacent epoxides in place of tetrahydrofuran moiety.
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■ Syntheses of (±)-4-Amino-1,3,4,5-tetrahydrobenz[cd]indole-4-carboxylic Acid, (±)-4-N,N-Dipropylamino-4-hydroxymethyl- and (±)-4-Propyloxy-1,3,4,5-tetrahydrobenz[cd]indole
Masanori Somei,* Naokatsu Aoki, and Kyoko Nakagawa
*Faculty of Pharmaceutical Sciences, Kanazawa University, 13-1 Takara-machi, Kanazawa 920-0934, Japan
Abstract
Simple syntheses of the title compounds are reported starting from indole-3-carboxaldehyde.
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■ Highly Asymmetric Induction in the Diels-Alder Reaction of 3-Alkoxycarbonyl-substituted
Katsuo Ohkata, Tomotaka Kubo, Keiko Miyamoto, Makiko Ono, Junko Yamamoto, and Kin-ya Akiba*
*Department of Chemistry, Faculty of Science, Hiroshima University, 1-3-1 Kagamiyama, Higashi-Hiroshima, Hiroshima 739-8526, Japan
Abstract
The asymmetric Diels-Alder reactions of 3-alkoxycarbonyl-substituted chromones (1c) with 2,3-dimethyl- and 2-methyl-1,3-butadienes in the presence of ZnCl2 at ambient temperature afforded the adducts (3c and 4b) with high diastereofacial selectivity (>98%) in high yield.
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■ Regioselective Prenylation of Phenols by Palladium Catalyst: Syntheses of Prenylphenols and Chromans
Masao Tsukayama,* Makoto Kikuchi, and Yasuhiko Kawamura
*Department of Chemical Science and Technology, Faculty of Engineering, University of Tokushima, Minamijosanjima-cho, Tokushima 770-8506, Japan
Abstract
The palladium-catalyzed coupling reaction of iodophenols (1) with 2-methyl-3-butyn-2-ol gave alkynylphenols (2). Catalytic hydrogenation of 2 over Raney nickel and the subsequent dehydration of the resultant alkylphenols (3) gave regioselectively the desired prenylphenols (4). Dehydration of alkylphenols (3f-h) gave chromans (7).
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■ Lewis Acid Promoted Tandem [4+2] Cycloaddition-Rearrangement Process — A Simple and Efficient Synthesis of Highly Functionalized Oxabicyclo[3.3.1]nonanes
Masahiro Toyota, Yoshihiro Wada, Youichi Nishikawa, Toshihiro Wada, and Keiichiro Fukumoto*
*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan
Abstract
Catalytic Lewis acid promoted tandem [4+2]cycloaddition-rearrangement processes of the trienic esters (4), (8) and (9) are reported. The novel tandem reactions proceed under thermal (110 °C, aluminum catalyst) conditions and afford the highly functionalized oxabicycl[3.3.1]nonanes (5), (10) and (11), respectively.
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■ Novel Rearrangement of the Trioxane Ring System of the Antimalarial Arteether upon Treatment with Acid in an Aqueous Methanol Solvent System
John K. Baker* and Hsien Tao Chi
*Department of Medicinal Chemistry and the Research Institute of Pharmaceutical Sciences, School of Pharmacy, University of Mississippi, University, Mississippi 38677, U. S. A.
Abstract
While arteether does not have a uv-chromophore, the treatment of arteether with a HCl, water, methanol system has been previously proposed as a method of generating a uv-chromophore upon which to base a quantitative analysis. The present study demonstrates that the originally proposed structure for the product was not correct and that the reaction is far more complex than originally proposed. It was found that the reaction yields 5 different α,β-unsaturated ketones (A-1, A-2, A-3, A-4, and A-5; whose structures are reported here for the first time) that have strong uv chromophores and 4 additional products (new compounds B-1 and B-2; previously reported α-artemether and β-artemether) that do not have any significant chromophores. The structure and stereochemistry of these novel reaction products were determined using thermospray hplc/ms, 1H-nmr, 13C-nmr, and two-dimensional nmr methods.
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■ Intramolecular Diels-Alder Reaction of Furans with Allenyl Ethers: High Effect of the Chain Length on the Structure and Reactivity of the Cycloadducts
Hsien-Jen Wu,* Shie-Hsiung Lin, and Chu-Chung Lin
*Department of Applied Chemistry, National Chiao Tung University, Hsinchu, 30050, Taiwan, R.O.C.
Abstract
The structure and reactivity of the cycloadducts of the title reaction were found to be highly dependent on the chain length between the furan diene and the allenyl ether dienophile. Reaction of the propargyl ether (2) with t-BuOK in t-BuOH at 85 °C for 3 h gave a mixture of the cycloadducts (3) and (4) in 90% yield, which were transferred to the benzo derivatives (5), (6) and (7). Treatment of the propargyl ether (8) with t-BuOK in t-BuOH at 85 °C for 5 h gave the products (9) and (10) in a ratio of 8:1 in 65% yield, no detectable amount of the cycloadduct (8b) was obtained. Refluxing of the propargyl ether (13) with t-BuOK in t-BuOH at 85 °C for 4 h gave the allenyl ether (14). Heating 14 in DMSO at 150 °C for 12 h still did not give 15.
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■ Synthesis of 4H-Pyrrolo[2,1-c][1,4]benzothiazines and N-Methyl-1,3,4,5-tetrahydro-2H-3-benzazepin-2-ones
Huey-Min Wang, Meng-Chiao Lin, and Ling-Ching Chen*
*Graduate Institute of Pharmaceutical Sciences, Kaohsiung Medical College, 100 Shih Chen 1st Rd., Kaohsiung 80708, Taiwan, R.O.C.
Abstract
Pummerer-type reaction was carried out with α-acyl sulfides and phenyliodine (III) bis(trifluoroacetate) instead of a-acyl sulfoxides to prepare 4H-pyrrolo[2,1-c][1,4]benzothiazines and N-methyl-1,3,4,5-tetrahydro-2H-3-benzazepin-2-ones.
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■ Compared Reactivity of 3-, 5-, 6-, and 8-Aminoimidazo[1,2-a]pyridines in Combes Reaction: Access to Imidazonaphthyridines and Dipyrido[1,2-a:3‘,2‘-d]imidazole
Yves Blache, Alain Gueiffier,* Olivier Chavignon, Henry Viols, Jean Claude Teulade, and Jean Pierre Chapat
*Laboratoire de Chimie Organique Pharmaceutique, URA-CNRS, Faculté de Pharamcie, Université Montpellier I, 15 Avenue Charles Flahault, 34060 Montpellier, France
Abstract
The synthesis of imidazo[1,2-a][1,8]naphthyridines and dipyrido[1,2-a:3‘,2‘-d]imidazole by treatment of aminoimidazo[1,2-a]pyridines following the Combes procedure is described.
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■ Stereoselective Synthesis of (±)-5-(1-Benzyloxyethyl)-6-(2-tert-Butyldiphenyloxyethyl)-2-piperidinone: A Formal Total Synthesis of Thienamycin
Shinji Tanimori,* Toshio Niki, Mingqi He, and Mitsuru Nakayama
*Department of Agricultural Chemistry, College of Agriculture, University of Osaka Prefecture, Sakai, Osaka 593-8531, Japan
Abstract
(±)-5-(1-Benzyloxyethyl)-6-(2-tert-butyldiphenyllsilyloxyethyl)-2-piperidinone (2), a synthetic intermediate for thienamycin (1), has been synthesized stereoselectively in nine steps from methyl 2-oxo-6-endo-methylbicyclo[3.1.0]hexane-1-carboxylate (3) using Lewis acid catalyzed homoconjugate addition of benzyl alcohol to 3 as a key step.
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■ Synthesis of Vinca Alkaloids and Related Compounds. Part LXIX. Synthesis of 15-Substituted Eburnane Derivatives
István Moldvai, Csaba Szántay Jr, and Csaba Szántay*
*Central Research Institute for Chemistry, Hungarian Academy of Sciences, H-1025 Budapest, P.O.Box 17, Hungary
Abstract
Starting from 15α-chlorovincamine (1), 15β-hydroxy-14-epivincamine (2a) and its 14-O-alkyl derivatives (2b, 2c) have been prepared via 14,15β-epoxyvincamine (3). The latter compound was transformed into (+)-15-oxodihydroeburnamine (6). The structures of 2-3 were established via detailed nmr investigations.a
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■ Synthesis and Biological Activities of New HMG-CoA Synthase Inhibitors: 2-Oxetanones with a Side Chain Containing Biphenyl, Terphenyl or Phenylpyridine
Hirokazu Hashizume,* Hajime Ito, Naoaki Kanaya, Hajime Nagashima, Hiroyuki Usui, Reiko Oshima, Munefumi Kanao, Hiroshi Tomoda, Toshiaki Sunazuka, Tohru Nagamitsu, Hidetoshi Kumagai, and Satoshi Omura
*Fuji Chemical Industries, Ltd., 530 Chokeiji, Takaoka, Toyama 933- 0951, Japan
Abstract
A series of 1233A analogs containing biphenylyl, terphenylyl or phenylpyridyl groups in their side chain were synthesized and tested for the inhibitory activities against 3-hydroxy-3-methylglutaryl coenzyme A (HMG-CoA) synthase and inhibition for the cholesterol biosynthesis in the mouse liver. The compounds with an oxetane, cyclobutanone or g-butyrolactone ring as isosters of a 2-oxetanone ring were entirely inactive. Among synthetic analogs, anti-4-[3-[2-(5-isopropyl-2-pyridyl)ethyl]phenyl]ethyl]-3-hydroxymethyl-2-oxetanone (10b) was most active in vitro. The structure-activity relationships on the transformations of 2-oxetanone and its side chain were obtained.
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■ A Synthesis of 7-Substituted 1H-Pyrano[4,3-b]quinoline Derivatives
Yutaka Azuma,* Atsuko Sato, and Mieko Morone
*Tohoku Pharmaceutical University, 4-4-1 Komatsushima, Aoba-ku, Sendai 981-8558, Japan
Abstract
The reaction of 4-chloro-3-ethynyl-6-methyl-2H-pyran-2-one (2) with aniline derivatives having a electron-donating group at the 3-position in EtOH gives 7-substituted 1H-pyrano[4,3-b]quinolin-1-one derivatives (3).
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■ An Alternative Synthesis of 2-Benzyloxy-6-hydroxymethyl-3-isobutyl-5-methoxypyrazine 4-Oxide, a Key Intermediate for Synthesis of OPC-15161
Satoshi Hashizume, Atsunori Sano, and Masahisa Oka*
*Tokyo Research Laboratories, Wako Pure Chemical Ind., Ltd., 1633 Matoba, Kawagoe, Saitama 350-1101, Japan
Abstract
2-Benzyloxy-6-hydroxymethyl-3-isobutyl-5-methoxypyrazine 4-oxide (5e), a key intermediate for synthesis of OPC-15161 (1a) having an inhibitory activity against superoxide anion generation, was prepared from 5-amino-2-benzyloxy-3-isobuyl-6-methoxycarbonylpyrazine 4-oxide (5b) by 3-step reaction.
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■ An Enantioselective Synthesis of (+)-Indolizidine 195B
Robert Bloch,* Cécile Brillet-Fernandez, Petra Kühn, and Gérard Mandville
*Laboratoire des Carbocycles, Associé au CNRS, Institut de Chimie Moleculaire d‘Orsay, Bat. 420, Université de Paris-Sud , 91405 Orsay Cedex, France
Abstract
A versatile enantioselective synthesis of the dendrobatid alkaloid (+)-indolizidine 195B is described, starting from the readily available lactol (1).
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■ Diels-Alder Reaction of 1,2,3-Triazine with Aldehyde Enamine
Junko Koyama,* Tamaki Ogura, and Kiyoshi Tagahara
*Kobe Pharmaceutical University, Motoyamakita, Higashinada, Kobe 658-8558, Japan
Abstract
The Diels-Alder reaction of 4-methyl-1,2,3-triazine with several aldehyde enamines was carried out to afford 2,5-disubstituted pyridines. As an application of this method, we accomplished the synthesis of alkaloid, fusaric acid.
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■ Intramolecular Nitrile Imine Cycloadditions to the Acetylenic Bond in the Synthesis of Pyrazolo[1,5-a][4,1]benzoxazepines and Pyrazolo[1,5-a][5,1]benzoxazocines
Gianluigi Broggini, Luisa Garanti, Giorgio Molteni, and Gaetano Zecchi*
*Dipartimento di Chimica Organicane Industriale , dell‘Universitè , Via Golgi 19, I-20133 Milano, Italy
Abstract
The intramolecular nitrile imine cycloaddition methodology has been applied to the construction of the title heterocyclic systems. The efficiency of this synthetic approach is rather variable, being markedly dependent on the kind of substitution at the acetylenic bond.
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■ Hydroisoquinoline Ring Construction via the Diels-Alder Reaction of Arecolone-derived Enole Silyl Ethers
Jian Ma, Masako Nakagawa,* Yasuhiro Torisawa, and Tohru Hino
*Faculty of Pharmaceutical Sciences, Chiba University, 1-33 Yayoi-cho, Inage-ku, Chiba 263-8522, Japan
Abstract
Diels-Alder reaction of the arecolone-derived siloxydienes (7, 14) was described. the hexahydroisoquinoline derivatives (21, 22, 23) were prepared from the reaction of 14 with methyl propiolate followed by Michael addition to the amido acrylates (18, 19, 20).
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■ Protonation and Sulfonation of Gramine in Strong Sulfuric Acid
Tine M. Fatum, Uffe Anthoni, Carsten Christophersen,* and Per H. Nielsen
*Marine Chemistry Section, The H. C. Ørsted Institute, University of Copenhagen, Universitersparken 5, DK-2100 Copenhagen, Denmark
Abstract
Gramine (3-dimethylaminomethylindole) when treated with concentrated sulfuric acid at room temperature, after protonation at the dimethylamino group and at position 3, was sulfonated at the aromatic positions. Initial sulfonation in either the 5- or 6-position was succeeded by introduction of a second sulfonic acid group giving a mixture of gramine-4,6-disulfonic acid, gramine-5,7-disulfonic acid and gramine-2,6- or gramine-2,5-disulfonic acid.
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■ Ketene Addition on Thienoanellated Thiazines and Thiazepines with Subsequent Ring Enlargement Reaction to Thieno[2,3-b][1,4]thiazocines and Thieno[2,3-b][1,4]thiazonines
Thomas Erker
*Institute of Pharmaceutical Chemistry, University of Vienna, Währinger Straße 10, A-1090 Vienna, Austria
Abstract
Reaction of alkylthiothieno[2,3-b][1,4]thiazine derivatives or alkylthiothieno[2,3-b][1,4]thiazepine derivatives (4, 5, 12, 16, and 24) with substituted acetyl chlorides in the presence of triethylamine led to azeto[1,2-d]thieno[2,3-d][1,4]thiazine derivatives and azeto[1,2-d]thieno[2,3-b][1,4]thiazepine derivatives. Some of them were ring opened by treatment with trifluoroacetic acid to give the thieno[2,3-b][1,4]thiazocine derivatives (27 - 30) and the thieno[2,3-b][1,4]thiazonine derivative (32), respectively. 6-Ethyl-1H-thieno[2,3-b][1,4]thiazine-2(3H)-thione (13), after reaction with α-chlorophenylacetyl chloride and triethylamine, afforded the thiazolo[2,3-b][1,4]thiazine derivative (34).
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■ Synthesis of N-Substituted Imidoethyl-3-aminomethyl-2,3-dihydro-1,4-dioxino[2,3-b]pyridines
Abdelhakim Benarab, Corinne Comoy, and Gérald Guillaumet*
*Laboratoire de Chimie Bioorganique et Analytique, URA-CNRS N° 499, Université d‘Orléans, BP 6759, Rue de Chartres, 45067 Orleans Cedex 2, France
Abstract
The multistep synthesis of N-substituted imidoethyl-3-aminomethyl-2,3-dihydro-1,4-dioxino[2,3-b]pyridines using as a final step the Mitsunobu reaction between aliphatic alcohols and imides is described.
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■ Synthesis of Nitro Derivatives of Triazoles
Ou Yuxiang,* Chen Boren, Li Jiarong, Dong Shuan, Li Jianjun, and Jia Huiping
*Department of Chemical Engineering, Beijing Institute of Technology, Beijing 100081, China
Abstract
This paper reviews the synthesis routes of nitro derivatives of triazoles with emphases on those used as energetic materials.