HETEROCYCLES
An International Journal for Reviews and Communications in Heterocyclic ChemistryWeb Edition ISSN: 1881-0942
Published online by The Japan Institute of Heterocyclic Chemistry
Special Issue
Kenji Koga's Special Issues, Vol. 66, No. 1, 2005
Published online: 22nd July, 2005
■ Wittig Rearrangement of Ally 2-Thiophenemethyl Ethers: Facile Synthesis of Thiophenemethanol and -ethanol Derivatives
Masayoshi Tsubuki,* Sohichiro Matsuo, and Toshio Honda*
*Institute of Medical Chemistry, Hoshi University, 2-4-41 Ebara, Shinagawa-ku, Tokyo 142-8501, Japan
Abstract
Wittig rearrangement of allyl 2-thiophenemethyl ethers was studied. Deprotonation of allyl 2-thiophenemethyl ethers (1a-d) occurred preferentially either the α- or the α’-position, depending on three kinds of BuLi. Thiophenemethanol and -ethanol derivatives were obtained as products of [2,3] and [1,2] sigmatropic rearrangements, respectively.
Published online: 2nd December, 2005
■ Direct C-C Coupling of meso-Octamethylcalix[4]pyrrole with 6-Nitroazolopyrimidines
Oleg N. Chupakhin,* Nadezhda A. Itsikson, Sergey Sh. Bashirov, Dmitry G. Beresnev, and Gennady L. Rusinov
*Institute of Organic Synthesis, Urals Branch, Russian Academy of Sciences, 20, S. Kovalevskaya st., Ekaterinburg, GSP-147, 620219, Russia
Abstract
It has been found that the reaction of meso-octamethylcalix[4]pyrrole with four equivalents of 6-nitroazolopyrimidine is accompanied by the C-C coupling of unsubstituted carbon atom in azines with β-position of pyrrole rings and results in the formation of tetrapyrimidine-substituted calix[4]pyrroles without introduction of any catalysts. Mono- and di-substituted calixpyrroles have been isolated.
Published online: 16th August, 2005
■ Synthesis of (-)-5-Epiindolizidine 167B and Formal Synthesis of 5E,9Z-Indolizidine 223AB
Naoki Toyooka* and Hideo Nemoto
*Faculty of Pharmaceutical Sciences, Toyama Medical and Pharmaceutical University, 2630 Sugitani, Toyama, Toyama 930-0194, Japan
Abstract
Synthesis of (-)-5-epiindolizidine 167B has been described using the highly stereoselective reduction of the enyne (2) as the key step.
Published online: 20th September, 2005
■ Heterocycles from Ylides. Part IX. A Convenient Synthesis of 1-Sulfonyl-2,3-disubstituted 2,3-Dihydroindoles
Giuseppe Cremonesi, Piero Dalla Croce,* and Concetta La Rosa
*Dipartimento di Chimica Organica e Industriale, Centro C. N. R., Università degli Studi di Milano, V. Venezian 21, I-20133 Milano, Italy
Abstract
The reaction of sulfur ylides (1) with N-(2-bromomethylphenyl)benzenesulfonamides (4) gives 2,3-dihydroindoles (5) whose structure and stereochemistry were assigned on the basis of analytical and spectroscopic data. Some chemical transformations of 5 are reported.
Published online: 11th October, 2005
■ Intermolecular Photoreaction of Benzenecarbothioamide with γ,δ-Unsaturated Ketones: Application to Synthesis of Cycloalkane [c]-Fused Pyridines
Kazuaki Oda,* Michiko Haneda, Naozumi Nishizono,* and Minoru Machida
*Faculty of Pharmaceutical Sciences, Health Sciences University of Hokkaido, Ishikari-Tobetsu, Hokkaido 061-0293, Japan
Abstract
Irradiation of benzenecarbothioamide with (2-methylenecycloalkyl)acetaldehyde in benzene gives cycloalkane [c]-fused pyridines in moderate yields.
Published online: 18th October, 2005
■ Dirhodium(II) Tetrakis[N-benzene-fused Phthaloyl-(S)-piperidinonate] as a Chiral Lewis Acid: Catalytic Enantioselective Aldol Reactions of Acetate-derived Silylketene Acetals and Aldehydes
Takuya Washio, Seiichi Nakamura, Masahiro Anada, and Shunichi Hashimoto*
*Graduate School of Pharmaceutical Sciences, Hokkaido University, Kita 12 Nishi 6, Kita-ku, Sapporo, Hokkaido 060-0812, Japan
Abstract
A first example of chiral dirhodium(II) complex-catalyzed enantioselective Mukaiyama aldol reactions is described. The aldol addition reaction of methyl acetate-derived trimethylsilylketene acetal with specific aldehydes such as benzyloxyacetaldehyde and electron-poor aromatic aldehydes is effectively catalyzed by dirhodium(II) tetrakis[N-benzene-fused phthaloyl-(S)- piperidinonate] (1a), providing silylated aldol adducts in up to 94% ee.
Published online: 4th October, 2005
■ Synthesis of 3-O-Alkylascorbic Acids from L-Ascorbic Acid in a Single Step
Yasuo Kikugawa,* Takeshi Sakamoto, Shinya Sato, and Kayoko Asami
*Faculty of Pharmaceutical Sciences, Josai University, 1-1 Keyakidai, Sakado, Saitama 350-0295, Japan
Abstract
An efficient single step synthesis of 3-O-alkylascorbic acids from ascorbic acid is described.
Published online: 18th October, 2005
■ Solvent Effect on the Reaction of 1-Methoxy-3-(2-nitrovinyl)indole with Nucleophiles
Koji Yamada, Tomoyuki Izumi, Fumio Yamada, and Masanori Somei*
*Division of Pharmaceutical Sciences, Graduate School of Natural Science and Technology, Kanazawa University, Kakuma, Kanazawa, Ishikawa 920-1192, Japan
Abstract
1-Methoxy-3-(2-nitrovinyl)indole (1a) functions as an electrophile and reacts with various nucleophiles. In THF, nucleophiles undergo conjugate addition to the β-carbon of the nitrovinyl side chain of 1a, regioselectively. The resultant Michael addition products (4d and 8) cyclize to novel 3-substituted 1-methoxyindoles (5 and 7) depending on reaction conditions and a plausible mechanism is discussed. In dipolar aprotic solvent (DMF), nucleophiles react with 1a at the 2-position predominantly with concomitant liberation of the 1-methoxy group giving 2-substituted indoles.
Published online: 1st November, 2005
■ Reactions of 1,1-Bis(silylmethyl)-1-alkene with N-Halosuccinimide and Ozone
Jun’ichi Uenishi,* Yusuke Tanaka, Masashi Ohmi, Hotsumi Shimomura, and Nobuyuki Kawai
*Kyoto Pharmaceutical University, Misasagi, Yamashina-ku, Kyoto 607-8412, Japan
Abstract
Electrophilic reactions of 3-phenyl-1,1-bis(trimethylsilymethyl)-1-propene (1) and 1,1-bis[dimethyl(phenyl)silylmethyl]-3-phenyl-1-propene (4) are described. Protodesilylation of 1 with PPTS gave 2-substituted allylsilane (2) in excellent yield. Halogenation of 4 with N-halosuccimide gave a mixture of 3-halo-5-phenyl-2-silylmethyl-1-pentene (5) and 3-halo-5-phenyl-1,2-bis(silylmethyl)-1-pentene (6). The reaction of 1 and 4 with ozone gave no carbonyl compounds but gave 3-hydoxy-5-phenyl-2-silylmethyl-1-pentene (7).
Published online: 18th October, 2005
■ Asymmetric Mannich-Type Addition of Lithium Glycolates to Imines Producing 3-Hydroxy-4-phenylazetidin-2-ones
Hiroki Fujieda, Seiji Hata, Ken-ichi Yamada, and Kiyoshi Tomioka*
*Graduate School of Pharmaceutical Sciences, Kyoto University, 46-29 Yoshida-shimoadachi-machi, Sakyo-ku, Kyoto 606-8501, Japan
Abstract
The external chiral ligand-controlled asymmetric Mannich-type reaction of a binary- or ternary-complexed lithium ester enolate of protected glycolates with benzaldehyde imines gave the corresponding 3-trialkylsilyloxy-4-phenylazetidin-2-ones, applicable as a synthetic intermediate of C13 side chain of taxan anticancer drugs, in moderate enantioselectivity.
Published online: 21st October, 2005
■ One-Step Synthesis of Ethyl Quinaldates by Lewis Acid Catalyzed Three-Component Coupling Reaction of Aromatic Amines, Aliphatic Aldehydes and Ethyl Glyoxylate
Takashi Inada, Takayuki Nakajima, and Isao Shimizu*
*School of Science and Engineering, Waseda University, 3-4-1 Okubo, Shinjuku-ku, Tokyo 169-8555, Japan
Abstract
A convenient, efficient and simple one-pot method for the synthesis of quinaldates was developed by three-component coupling reaction of an arylamine (1), ethyl glyoxylate and an aliphatic aldehyde (2) in the presence of Lewis acid catalyst. The reaction proceeded most effectively using Yb(OTf)3 as a catalyst.
Published online: 14th October, 2005
■ Palladium-catalyzed Cyclocotrimerization of Propargyl Alcohols with Aryl Halides
Shuichi Oi,* Hideki Orihara, Hiroshi Kawai, and Yoshio Inoue*
*Graduate School of Engineering, Tohoku University, Aramaki, Aoba-ku, Sendai 980-8578, Japan
Abstract
Tertiary propargyl alcohols react with aryl halides in the presence of K2CO3 and a catalytic amount of palladium(0) complex affording 2:1 cyclocotrimerization products, 3-benzylidene-2,3-dihydrofuranes (3).
Published online: 15th November, 2005
■ Radical Reactions and α-Silylations of Optically Active 4-Trichloromethyl-β-lactone
T. Andrew Mitchell and Daniel Romo*
*Department of Chemistry, Texas A & M University, College Station, Texas 77843-3255, U.S.A.
Abstract
Radical alkylations and α-silylations of optically active (R)-4-trichloromethyl-2-oxetanone are described that maintain the integrity of the β-lactone. Alternate methods for selective dechlorinations of both the β-lactone and the derived Weinreb amide are described.
Published online: 21st October, 2005
■ Spiro Crown Ethers Bearing (S)-1,1’-Spirobiindanes as Chiral Backbones
Kohji Yonezawa, Mahesh L. Patil, Hiroaki Sasai, and Shinobu Takizawa*
*The Institute of Scientific and Industrial Research, Osaka University, 8-1, Mihogaoka, Ibaraki, Osaka 567-0047, Japan
Abstract
The synthesis of spiro chiral crown ethers ((S)-1a) and ((S)-1b) has been achieved. The combination of (S)-1a and KOH promoted the asymmetric alkylation of glycine derivative (2) with moderate enantioselectivity.
Published online: 22nd November, 2005
■ Hetero-Diels-Alder Reaction Catalyzed by Self-organized Polymeric Rare Earth Complexes under Solvent-free Conditions
Shuichi Ishida, Tetsuji Hayano, Hiroshi Furuno, and Junji Inanaga*
*Synthetic Methodology and Catalysis, Institute for Materials Chemistry and Engineering (IMCE), Kyushu University, 6-10-1 Hakozaki, Higashi-ku, Fukuoka 812-8581, Japan
Abstract
2-Substituted 2,3-dihydropyran-4-one derivatives were conveniently synthesized under solvent-free conditions by Lewis acid-catalysis with a polymeric scandium sulfonate complex, which can be prepared in a self-organized manner in one step and successfully reused for the next round of reactions.
Published online: 15th November, 2005
■ Two New Indole Alkaloids from Aspidosperma subincanum and Geissospermum vellosii
Haruaki Ishiyama, Miyako Matsumoto, Mitsuhiro Sekiguchi, Hideyuki Shigemori, Ayumi Ohsaki, and Jun’ichi Kobayashi*
*Graduate School of Pharmaceutical Sciences, Hokkaido University, Kita 12 Nishi 6, Kita-ku, Sapporo, Hokkaido 060-0812, Japan
Abstract
Two new indole alkaloids, subincanadine G (1) and pausperadine A (2), were isolated from the barks of Aspidosperma subincanum Mart and Geissospermum vellosii Allemão, respectively. Subincanadine G (1) has 1-azoniatricyclo[4.3.3.01,5]undecane moiety, while pausperadine A (2) contains an N-oxide moiety. The gross structures and relative stereochemistry of 1 and 2 were elucidated by spectroscopic data.
Published online: 28th October, 2005
■ Synthesis of N-Methylphenanthridinone Derivatives Fused with a Silacyclohexane Ring by Radical Reaction Using Tributyltin Hydride
Yuya Hoshino and Osamu Hoshino*
*Faculty of Pharmaceutical Sciences, Science University of Tokyo, 2641 Yamazaki, Noda, Chiba 278-8510, Japan
Abstract
Radical reaction of (N-methyl-7-bromo-2,2-dimethyl-2-silatetralin-6-ylamino)veratramide (8a) and -piperonamides (8b) in boiling benzene using tributyltin hydride and AIBN gave two kinds of N-methylphenanthridinone derivatives (15 and 16), which were cyclized at 6- and 2-positions of aroylic acid moiety. On the other hand, similar reaction of N-methyl-N-(2-bromoveratryl and 2-bromopiperonyl)-2,2-dimethyl-2-silatetralin-6-carboxamides (14) produced N-methylphenanthridinone deivatives (17) as each sole product, in which cyclization occurred at 5-position of 2-silatetralin moiety.
Published online: 15th November, 2005
■ The Structural Information of the Quaternary Ammonium Salts Derived from Nicotine and Sparteine in the Solid State
Kazuhiro Yoshizawa, Yasuko In, Toshimasa Ishida, and Takayuki Shioiri*
*Graduate School of Environmental and Human Sciences, Meijo University, Shiogamaguchi, Tempaku, Nagoya 468-8502, Japan
Abstract
Preparation and X-Ray crystallographic analysis of the benzyl quaternary salts of nicotine and sparteine were described.
Published online: 29th November, 2005
■ Are Multicomponent Strecker Reactions of Diketones with Diamines under High Pressure Amenable to Heterocyclic Synthesis?
Koji Kumamoto, Hirokazu Iida, Hiroshi Hamana, Hiyoshizo Kotsuki,* and Kiyoshi Matsumoto,*
*Faculty of Pharmaceutical Sciences, Chiba Institute of Science, 3 Shiomi-cho, Choshi, Chiba 288-0025, Japan
Abstract
Employing double Strecker strategy, two new heterocyclic compounds, 5,6,11,12-tetrahydro-6,11-dimethyldibenzo[b,f][1,4]diazocine-6,11-dicarbonitrile and 1,2,3,4,5,10-hexahydrophenazine-4a,10a-dicarbonitrile, were prepared in one step albeit in low yields. The reaction has proven to be very limited, but such a sterically hindered amine as N-methylaniline underwent Strecker reaction with benzaldehyde and TMSCN to give the corresponding α-amino nitriles.
Published online: 18th November, 2005
■ Preparation of N-Sulfonyl-2-quinolinone Using Ring-closing Metathesis (RCM)
Mitsuhiro Arisawa,* Chumpol Theeraladanon, and Atsushi Nishida*
*Graduate School of Pharmaceutical Sciences, Chiba University, 1-33 Yayoi-cho, Inage-ku, Chiba 263-8522, Japan
Abstract
An efficient method for the preparation of N-sulfonyl-2-quinolinone using ring-closing metathesis (RCM) is described.
Published online: 4th October, 2005
■ Anion Receptors
Oleg N. Chupakhin,* Nadezhda A. Itsikson, Yuri Yu. Morzherin, and Valery N. Charushin
*Institute of Organic Synthesis, Urals Branch, Russian Academy of Sciences, 20, S. Kovalevskaya st., Ekaterinburg, GSP-147, 620219, Russia
Abstract
The review outlines the recent achievements in the field of anion coordination chemistry, and is focusing on the function-oriented design of anion-binding “host” ligands. Comparative analysis of receptor abilities for various classes of organic compounds towards anions is presented.
Published online: 4th October, 2005
■ Enantiotopic Synthesis of Natural Products: Merrilactone and Guanacastepene
Heedong Yun, Zhaoyang Meng, and Samuel J. Danishefsky*
*Department of Chemistry, Columbia University, 3000 Broadway, New York, NY 10027, U.S.A.
Abstract
We have previously disclosed the total syntheses of racemic merrilactone A and guanacastepene A. We describe herein the development of new routes to key intermediates in the first-generation syntheses, which will allow us to access both merrilactone A and guanacastepene A in enantiomerically enriched form.
Published online: 1st November, 2005
■ Synthetic Strategies of Fostriecin
Masakatsu Shibasaki* and Motomu Kanai
*Faculty of Pharmaceutical Sciences, University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan
Abstract
Fostriecin is a naturally occurring triene-containing phosphate ester, which exhibits a potent and selective PP2A inhibitory activity. Due to its interesting chemical structure and biological activity, strategically unique total syntheses of fostriecin were reported from several groups. An overview of the synthesis and chemistry-based structure-activity relationships of fostriecin is described in this review.
Published online: 15th November, 2005
■ Expanding Structural Diversity of Terpene Trilactones from Ginkgo biloba Extract: Studies towards Core-modified Ginkgolides
Sergei V. Dzyuba,* Sergei Bolshakov, Jean Li, and Koji Nakanishi*
*Department of Chemistry, Columbia University, 3000 Boradway, New York, NY 10027, U.S.A.
Abstract
Ginkgolides, the unique terpene trilactones from the Ginkgo biloba tree, are believed to enhance memory, improve blood circulation and exhibit beneficial effects in the treatment of dementia. Unfortunately, mechanisms of ginkgolide actions at the molecular level are still not determined. Ginkgolide skeleton modifications may provide a plausible approach to address subtle changes in the ligand-receptor interactions. Furthermore, the simplified structure of the ginkgolide skeleton may guide to the leads that will be attractive for drug development. This review covers the modifications of the ginkgolide skeleton, reported to date.