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
Yoshio Ban's Special Issues, Vol. 42, No. 1, 1996
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■ Total Synthesis of Mycalamide A. Further Synthetic Study of the Right Half
Tadashi Nakata, Hideto Fukui, Tadakiyo Nakagawa, and Hiroko Matsukura
*The Institute of Physical and Chemical Research, Wako-shi, Saitama 351-0198, Japan
Abstract
The right half 5 of mycalamide A (1) was synthesized starting from (R)- or (S)-pantolactone via the Sharpless asymmetric dihydroxylation as the key step. The total synthesis of mycalamide A (1) was accomplished by coupling of the right and left halves.
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■ Cyclobutane Strategy for the Synthesis of A-Ring Aromatic Trichothecanes
Hideo Nemoto, Junji Miyata, and Keiichiro Fukumoto
*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan
Abstract
A novel synthesis of A-ring aromatic trichothecane (2) by the regiocontrolled cyclization of 5-hydroxy-2-(2-methoxymethoxy-4-methylphenyl)-2-methyl-1-methylidenecyclopentane (10), which was prepared via the 2-phenylcyclobutanone (6) and cyclobutanols (7 and 8) and the 2-methylidene-3-phenylcyclopentanone (9), was achieved.
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■ Lipase AH-Catalyzed Asymmetric Synthesis of (S)-(-)-NB 818
Yukiyoshi Yamazaki and Kazuo Achiwa
*Schol of Pharmaceutical Sciences, University of Shizuoka, 52-1 Yada, Shizuoka 422-8526, Japan
Abstract
The first lipase-catalyzed asymmetric synthesis of biologically active (S)-(-)-NB818, has been achieved.
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■ Synthesis, Conformational Analysis and Biological Evaluation of 2-(5-Deoxy-β-D-ribofuranosyl)pyridine-4-carboxamide
Pieter E. Joos, Alex De Groot, Eddy L. Esmans, Frank C. Alderweireldt, André De Bruyn, Jan Balzarini, and Erik De Clercq
*University of Antwerp (RUCA), Department of Chemistry, Groenenborgerlaan 171, B-2020 Antwerp, Belgium
Abstract
Coupling of 5-deoxy-2,3-O-isopropylidene-D-ribono-1,4-lactone (5) with 2-lithio-4-(4,5-dihydro-4,4-dimethyloxazol-2-yl)pyridine (6), subsequent mesylation, followed by reduction and ammonolysis resulted in the formation of 2-(5-deoxy-β-D-ribofuranosyl)pyridine-4-carboxamide (4). The anomeric configuration was established with 2D-NOESY-1H-nmr-spectroscopy. Conformational analysis was done with the aid of the high resolution 1H-nmr-spectroscopy data. Compound (4) possessed modest cytostatic activity against a number of tumor cell lines and was slightly inhibitory to vaccinia virus and vesicular stomatitis virus.
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■ Studies on Organometallic Compounds. IX. Synthesis of Bipyridine N-Oxides and Terpyridines by Palladium Catalyzed Cross-Coupling Reaction of Trimethylstannylpyridines with Bromopyridines
Yutaka Yamamoto, Takuo Tanaka, Masayoshi Yagi, and Masayuki Inamoto
*Tohoku Pharmaceutical University, 4-4-1 Komatsushima, Aoba-ku, Sendai 981-8558, Japan
Abstract
Reaction of trimethylstannylpyridines with bromopyridines in the presence of Pd(PPh3)4 directed toward a practical use was accomplished, giving all nine pyridinylpyridine N-oxides in satisfactory yields. Similarly, nicotelline and 2,2’:6’,2”-terpyridine were produced in good yields.
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■ A Synthesis of the Derivatives of 1,2,3,5,10,10a-Hexahydrobenz[f]indolizine-6,9-dione Having Antifungal Activity as a Simple Model of SaframycinA
Akinori Kubo, Tatsuya Nakai, Yuichi Koizumi, Yoshiyasu Kitahara, Naoki Saito, Yuzuru Mikami, Katsukiyo Yazawa, and Jun Uno
*Meiji Pharmaceutical University, 2-522-1 Noshio, Kiyose, Tokyo 204-8588, Japan
Abstract
A simple and efficient synthesis of 1,2,3,5,10,10a-hexahydrobenz[f] indolizine-6,9-dione (7) and its analogs (28-30) is described starting from the corresponding lactam (15b).
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■ A Convenient Route to the Imidazo[4,5-b]pyridines
Kenichi Harada, Tominari Choshi, Eiichi Sugino, Koichi Sato, and Satoshi Hibino
*Faculty of Pharmacy and Pharmaceutical Sciences, Fukuyama University, Fukuyama, Hiroshima 729-02, Japan
Abstract
The reaction of the acroleins possessing a leaving group, derived from alkenyl sulfides by Vilsmeier reaction, with 4-amino-1-methylimidazole provided a new and convenient route to the imidazo[4,5-b]pyridines, the reaction mechanisms of which were examined by a deuterium labelled experiment.
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■ Syntheses of L-Phenylalanine Derivatives Containing a Sulfur Substituent at the 2-Position
Masashi Ohba, Masaaki Imasho, and Tozo Fujii
*Faculty of Pharmaceutical Scicences, Kanazawa University, 13-1 Takara-machi, Kanazawa 920-0934, Japan
Abstract
A full account is given of the chiral syntheses of sulfur-containing L-phenylalanine derivatives (8b,c), selected as key intermediates for the synthesis of models for the starfish alkaloid imbricatine (7), via a 5-step route starting from N,N-diethyl-3,5-dimethoxybenzamide (9). The key steps involve introduction of a sulfur substituent into 9 at the 2-position and construction of the chiral α-amino acid moiety in the chlorides (12b,c) by the “bis-lactim ether” method.
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■ Practical Total Syntheses of Physostigmines and of Phenserines: A Synopsis
Xue-Feng Pei, Qian-sheng Yu, Bao-yuan Lu, Nigel H. Greig, and Arnold Brossi
*Department of Chemistry, Georgetown University, Washington DC 20057, and Scientist Emeritus NIH, USA
Abstract
(±)-1,3-Dimethyl-3-cyanomethyl-5-methoxyoxindole (8), or (3S)-enriched 8 obtained by asymmetric alkylation, separated into the optically pure enantiomers (8a) and (8b) when chromatographed on a microcrystalline cellulose triacetate (MCTA) column. Asymmetric alkylation of (±)-1,3-dimethyl-5-tetrahydropyranyloxyoxindole (6) gave the nitrile (9) ((3S) 66 % ee) which could not be separated on the MCTA column. Optically pure eseroline (17a) was obtained by recrystallization of the fumarate salt (66 % ee) obtained from 9 after reduction with Vitride, reductive N-methylation, and treatment with 2N HCl.
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■ Two New Bisacridone Alkaloids from Citrus Plants1
Motoharu Ju-ichi, Yuko Takemura, Noriko Nagareya, Mitsuo Omura, Chihiro Ito, and Hiroshi Furukawa
*Faculty of Pharmaceutical Science, Mukogawa-Women's University, 11-68 Koushien Kyuban-Cho, Nishinomiya, Hyogo 663-8179, Japan
Abstract
Two new binary acridone alkaloids named citbismine-D (1) and -E (2) were isolated from the roots of Marsh grapefruit (Citrus paradisi). The structures were elucidated by spectroscopic studies as 1 and 2. Citbismine-E (2) was also obtained from the roots of Hirado-Buntan (C. grandis).
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■ Diastereomeric Preparation of α- and β-Phenylthio Substituted N-Acylpyrazoles
Choji Kashima, Katsumi Takahashi, and Akira Hosomi
*Department of Chemistry, University of Tsukuba, 1-1-1 Ten-nodai, Tsukuba-shi, Ibaraki, 305-8571, Japan
Abstract
When 3-phenyl-l-menthopyrazole was used as a chiral auxiliary, the diastereomeric preparation of α- and β-phenylthio-substituted N-acylpyrazoles (4 and 9) was accomplished in high yield by the α-sulfenylation using diphenyl disulfide and the conjugate addition of thiophenol, respectively.
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■ Synthesi of Aminobenzo[b]pyrrolizinone and Aminobenzo[b]indolizinone Derivatives
Masanao Taga, Hisao Ohtsuka, Isao Inoue, Takayuki Kawaguchi, Sumihiro Nomura, Koichiro Yamada, Tadamasa Date, Hajime Hiramatsu, and Yasuhiko Sato
*Organic Chemistry Research Laboratory, Tanabe Seiyaku Co.Ltd., 2-2-50, Kawagishi, Toddda, Saitama 335-8505, Japan
Abstract
The fused tricyclic indole derivatives (4a and 4b-1~4b-7) possessing an amino function on the benzo[b]pyrrolizinone or the benzo[b]indolizinone skeleton were synthesized via intramolecular reductive cyclization and Curtius rearrangement, and these compounds exhibited anti-anoxia activity.
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■ Reaction of 3-Aralkylsulfonyl-2-(N-cyanoimino)-thiazolidines with Oxygen Nucleophiles
Tetsuaki Tanaka, Yumi Nakamoto, Kaori Maekawa, Mayumi Watanabe, Chihiro Nishihara, Chuzo Iwata, and Shuji Uchida
*Faculty of Pharmaceutical Sciences, Osaka University, 1-6 Yamadaoka, Toyonaka, Osaka 560-0043, Japan
Abstract
3-Aralkylsulfonyl-2-(N-cyanoimino)thiazolidines react with oxygen nucleophiles, such as sodium alkoxides and carboxylates, at the 3-sulfonyl group to give 3-alkyl- and 3-acyl-2-(N-cyanoimino)thiazolidines, respectively.
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■ α-Amino Ketone Synthesis from Aldehydes and N-(α-Dialkylaminoalkyl)benzotriazoles
Alan R. Katritzky, Dai Cheng, and Richard P. Musgrave
*Center for Heterocyclic Compounds, Department of Chemistry, University of Florida, P. O. Box 117200, Gainesville, FL 32611-7200, U.S.A.
Abstract
Thiazolium salt-catalyzed reactions of aldehydes with morpholino-(alkylbenzotriazoles) allow the synthesis of a variety of α-amino ketones. The relationship between reaction conditions and selectivity is discussed.
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■ The First and Simple Synthesis of Indole Alkaloid, Bipolaramide
Masanori Somei and Toshiya Kawasaki
*Faculty of Pharmaceutical Sciences, Kanazawa University, 13-1 Takara-machi, Kanazawa 920-0934, Japan
Abstract
The first and simple total synthesis of bipolaramide was achieved in 31% overall yield from (2S)-2,3-dihydroindole-2-carboxytic acid in three (or two) steps. Derivatives of bipolaramide having halogen, alkenyl, nitro, or azido substituents were also prepared.
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■ Synthesis of Novel Heterocycle-fused Furo[3,4-d]isoxazoles via Ring Transformation of 2-Isoxazoline-2-oxides by Lewis Acid
Kazuho Harada, Eisuke Kaji, Kuniaki Sasaki, and Shonosuke Zen
*School of Pharmaceutical Sciences, Kitasato University, Shirokane, Minato-ku, Tokyo 108-8641, Japan
Abstract
Reaction of five-membered heterocycle-substituted 2-isoxazoline-2-oxides (2, 3, and 4) with titanium tetrachloride afforded novel heterocycle-fused furo[3,4-d]isoxazoles (5, 6 and 7), respectively. This transformation was applied to indole-substituted 2-isoxazoline-2-oxide (8) to give the corresponding fused furo[3,4-d]isoxazole (9) and indolo[2,3-b]-1-pyrroline-1-oxide (10).
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■ Enantiopsecific Ring Expansion of Oxetanes: Stereoselective Synthesis of Tetrahydrofurans
Katsuji Ito, Miwa Yoshitake, and Tsutomu Katsuki
*Department of Chemistry, Faculty of Science, Kyushu University, 6-10-1 Hakozaki, Higashi-ku, Fukuoka 812-8581, Japan
Abstract
Enantiospecific ring expansion of oxetanes to tetrahydrofurans with diazoacetic acid ester was found to be catalyzed by the copper complex of (7R,7’R)-7,7’-di(1-tert-butyldimethylsiloxy-1-methylethyl)-6,6’,7,7’-tetrahydro-5H,5’H-2,2’-bi-1,1’-pyrindine (4). For example, the reaction of (R)-2-phenyloxetane of 89% ee and tert-butyl diazoacetate with Cu-4 complex as a catalyst provided (2S,3R)-tert-butyl 3-phenyltetrahydrofuran-2-carboxylate of 92% ee as a major product, while that of (S)-2-phenyloxetane of 85% ee provided (2S,3S)-tert-butyl 3-phenyltetrahydrofuran-2-carboxylate of 93% ee as a major one.
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■ Tenuilobine - A New Polyamine Alkaloid from Oncinotis tenuiloba
Martin K. -H. Doll, Armin Guggisberg, and Manfred Hesse
*Organisch-chemisches Institut, Universität Zürich, Winterthurerstrasse 190, 8057 Zürich, Switzerland
Abstract
A new cross-linked polyamine alkaloid, named tenuilobine (1), was isolated from the leaves of Oncinotis tenuiloba (Apocynaceae), the structure was established by spectroscopic means. It is the first natural alkaloid containing spermine and spermidine as polyamine parts. Presumably, compound (1) is involved in the biosynthesis of the macrocyclic spermidine alkaloids with lactam groups.
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■ Briarane Diterpenes from Micronesian Gorgonians
Mark T. Hamann, Karl N. Harrison, Anthony R. Carroll, and Paul J. Scheuer
*Department of Chemistry, University of Hawaii at Manoa, 2545 Tha Mall, Honolulu, Hawaii 96822-2275, U.S.A.
Abstract
Four new briaranes, nui-inoalides A-D, (6-9) are described. They were isolated from octocorals collected in Pohnpei and Ant atoll, Micronesia. The absolute stereochemistry of the known briarane juncin E (5) was determined. Nuiinoalide A (6) and the known gemmacolides A, B, and D (2-4) exhibit immunomodulatory activity.
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■ Hetericyclization of 5-Trifluoroacetyltricyclo-[4.3.1.13,8]undecan-4-one to Some 6- and 7-Membered Nitrogen Heterocycles
Shoji Eguchi, Akira Umada, and Takashi Okano
*Institute of Applied Organic Chemistry, Faculty of Engineering, Nagoya University, Chikusa, Nagoya, Aichi 464-8601, Japan
Abstract
Heterocyclization study of 5-trifluoroacetyl[4.3.1.13,8]undecan-4-one into pyrimidine, pyridine, and 1,4-diazepine derivatives as a route to trifluoromethylated homoadamantanefused 6- and 7-membered nitrogen heterocycles is reported.
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■ Effect of Bromides on the Anomalous Photoarylation of 5-Halo-1,3-dimethyluracils
Koh-ichi Seki, Kazue Ohkura, Yuki Fukai, and Masanao Terashima
*Faculty of Pharmaceutical Sciences, Health Sciences University of Hokkaido, Ishikari-Tobetsu, Hokkaido 061-0293, Japan
Abstract
Photolysis of 5-chloro- and 5-fluoro-1,3-dimethyluracil in toluene in the presence of a bromide (e.g.,p-dibromobenzene, 1,2-dibromoethane, and benzyl bromide) and an acid (hifluoroacetic acid, HBr) afforded 1,3-dimethyl-5-tolyluracils and the 6-isomers as the isomeric mixture. 5-Arylation occurred most favorably at ortho, while meta-isomers were preferential products in 6-arylation. The 5-isomers are suggested to be derived from uracils excited in the singlet states, while the 6-isomers are presumed to result from the uracils excited in the triplet states.
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■ Asymmetric Pictet-Spengler Reaction Using α-Methylbenzylamine as a Chiral Auxiliary Group
Than Soe, Tomohiko Kawate, Naoko Fukui, Tohru Hino, and Masako Nakagawa
*Faculty of Pharmaceutical Sciences, Chiba University, 1-33 Yayoi-cho, Inage-ku, Chiba 263-8522, Japan
Abstract
The Pictet-Spengler reaction of chiral N-(β-3-indolyl)ethyl-α-methylbenzylamine with aldehydes in the presence of acids in refluxing benzene provided 1-substituted tetrahydro-β-carbolines (~72 % de).
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■ Total Synthesis of the Major Metabolites of Gomisin A. Synthesis of Homochiral Met A-II, Met A-III, and Met F
Masahide Tanaka, Hiroshi Mitsuhashi, Masao Maruno, and Takeshi Wakamatsu
*Central Research Laboratory, Tsumura & Co., 3586 Yoshiwara, Ami-machi, Inashiki-gun, Ibaraki, 300-11, Japan
Abstract
The total syntheses of the metabolites of gomisin A (1) were achieved. By the Mukaiyama hydration or the successive double bond migration, lactone ring reduction, glycol formation, and reduction, the homochiral lactones (10a-c) provided met A-III (3), A-II (2), D (5), and F (7).
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■ Synthesis of 5-Substituted Pyrimidine Nucleosides through a Palladium-catalyzed Cross-Coupling of Alkenylhalosilanes
Hayao Matsuhashi, Yasuo Hatanaka, Manabu Kuroboshi, and Tamejiro Hiyama
*Research Laboratory of Resources Utilization, Tokyo Institute of Technology, 4259 Nagatsuta-cho, Midori-ku, Yokohama 226-8503, Japan
Abstract
Palladium-catalyzed cross-coupling of alkenylhalosilanes with 5-iodouracil and 5-iodouridine derivatives was described. 5-Iodo-1,3-dimethyluracil coupled with alkenylfluorodimethylsilanes to give the corresponding cross-coupled products in good yield. Fully protected 5-iodo-2’-deoxyuridine derivative also underwent the cross-coupling reaction. Noteworthy is that unprotected 5-iodo-2’-deoxyuridine could be converted into the corresponding cross-coupled products in good yields using alkenyl(difluoro)methylsilanes.
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■ New Anionic Cyclization of 4- and 5-Alkynylamines: Synthesis of 2-Benzylidene Pyrrolidines and Piperidines
Masao Tokuda, Hirotake Fujita, Makoto Nitta, and Hiroshi Suginome
*Division of Molecular Chemistry, Graduate School of Engineering, Hokkaido University, Sapporo 060-8628, Japan
Abstract
Treatment of 4- and 5-alkynylamines with 0.5-1.2 equiv. of butyllithium brought about a facile anionic cyclization, giving the corresponding enamine pyrrolidines and piperidines having an exo double bond in high yields. Treatment of 4-alkynamides with lithium aluminum hydride also gave the similar enamine pyrrolidines in high yields.
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■ Total Syntheses of BE-12406 A and Its C(8)-Vinyl Analog
Takamitsu Hosoya, Eiji Takashiro, Yasuko Yamamoto, Takashi Matsumoto, and Keisuke Suzuki
*Department of Chemistry, Keio University, 3-14-1, Hiyoshi, Kohoku, Yokohama 223-8522, Japan
Abstract
Total syntheses of BE-12406 A (3a) and its C(8)-vinyl analog (3c) are described. The key step is the selective O-glycosylation of naphthol (4)with L-rhamnopyranosyl fluoride (5) by employing Cp2HfCl2-AgClO4 in fluorobenzene at -20°C in the presence of a hindered base, 2,6-di-t-butyl-4-methylpyridine (12), affording O-glycoside (11) in good yield.
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■ Preparation of Optically Active 8,8’-Disubstituted 1,1’-Biisoquinoline
Ken-ichi Hirao, Ryuta Tsuchiya, Yasuhiro Yano, and Hirohito Tsue
*Laboratory of Organic Chemistry, Graduate School of Environmental Earth Science, Hokkaido University, Sapporo 060-0810, Japan
Abstract
Synhesis of 1,1’-biisoquinolines having substituents in the 8,8’-positions and their resolution by hplc on a chiral column on a preparative scale are described.
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■ Enantioselective [2,3]-Wittig Rearrangement via a Chiral Boron Ester Enolate
Katsuhiko Fujimoto, Chiho Matsuhashi, and Takeshi Nakai
*Department of Chemical Technology, Faculty of Engineering, Tokyo Institute of Technology, Meguro-ku, Tokyo 152, Japan
Abstract
The first enantioselective [2,3]-Wittig rearrangement of α-(allyloxy)- acetates is described which involves a chiral boron enolate with a chiral bis-sulfonamide ligand to afford the α-hydroxy-β-alkyl-γ,δ-unsaturated esters in a high enantioselectivity (>95%ee), along with a high threo diastereoselectivity.
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■ The Synthesis of 1β-Fluorocarbapenem Derivative
Masataka Ihara, Ken Satoh, Yohhei Ishida, Nobuaki Taniguchi, Yuji Tokunaga, Makoto Takemura, and Keiichiro Fukumoto
*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan
Abstract
The synthesis of 1β-fluorocarbapenem derivative (16) was carried out starting with the 4-acetoxyazetidin-2-one (3) through the carbapenem formation utilizing the Sankyo’s procedure.
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■ Aloxylation at Meta Position to Hydroxyl Group of L-Tyrosine: Preparation of Alkyl (S)-2,4-Dialkoxyphenylalaninates
Hiroshi Hara, Tsutomu Inoue, Masaki Endoh, Hiroshi Nakamura, Hiroyuki Takahashi, and Osamu Hoshino
*Faculty of Pharmaceutical Sciences, Science University of Tokyo, 12, Ichigaya Funagawara-machi, Shinjuku-ku, Tokyo 162-0826, Japan
Abstract
Treatment of dienone lactone (2), derived from L-tyrosine, with methanol in the presence of boron trifluoride etherate gave methyl N-protected (S)-2,4-dimethoxyphenylalaninate (4) in 76 % yield. Similarly, two homologues (9 and 10) were conventionally produced from 2.