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
Sho Ito's Special Issues, Vol. 54, No. 1, 2001
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■ Bis(ethylenethio)tetraselenafulvalene and Related Hybrid Diselenadithiafulvalenes as Novel Electron Donors Forming Highly Conductive Complexes with 7,7,8,8-Tetracyanoquinodimethane
Mie Kodani, Satoshi Murakami, Tetsuya Jigami, Kazuo Takimiya, Yoshio Aso, and Tetsuo Otsubo*
*Department of Applied Chemistry, Faculty of Engineering, Hiroshima University, Higashi-hiroshima, Hiroshima 739-8527, Japan
Abstract
The title tetraselenafulvalene (BET-TSF) and four related hybrid diselenadithiafulvalenes (STF) have been synthesized as a five-membered heterocycle-fused tetrathiafulvalene type of novel electron donors, which form highly conducting molecular complexes with 7,7,8,8-tetracyanoquinodimethane. In particular, the complex of BET-TSF shows a room-temperature conductivity of 2600 S cm—1, which is of the highest class for a molecular complex.
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■ Thermolysis of Ethoxycarbonyl[2-phenyl-2-(phenylsulfonylhydrazono)ethyl]methylenetriphenylphosphoranes. Formation of Substituted Pyridazinones
Suketaka Ito,* Akikazu Kakehi, Kyoko Okada,1 and Ikuko Shibazaki
*Depatment of Indusrial Chemistry, Faculty of Engineering, Shinshu University, 4-17-1 Wakasato, Nagano 380-8553, Japan
Abstract
Ethoxycarbony[2-phenyl-2-(phenylsulfonylhydrazono)ethyl]methylenetriphenylphosphoranes were prepared by the reaction of ethoxycarbonymethylenetriphenylphosphorane with phenylsulfonylhydrazones of phenacyl bromides. Thermolysis of the phosphoranes gave 6-phenyl-2-phenylsulfonyl-3(2H)-pyridazinones, 6-phenyl-4-phenylsulfonyl-3(2H)-pyridazinones, and 6-phenyl-2-phenylsulfonyl-4-triphenylphosphoranylidene-1,4-dihydro-3(2H)-pyridazinones, together with triphenylphosphine. The structure of disubstituted methylenetriphenylphosphorane was confirmed by an X-Ray diffraction method.
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■ [22]Metacyclophanedienes with Furan Bridges
Reginald H. Mitchell,* Timothy R. Ward, and Yunxia Wang
*Department of Chemistry, University of Victoria, P.O. Box 3065, Victoria, BC V8W 3V6, Canada
Abstract
[22]Metacyclophanedienes with either one furan and one benzene or two furans on the bridges are thermally stable and do not convert to their isomeric dihydropyrenes, unlike the compounds with one furan or one benzene on the bridge.
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■ Total Syntheses of Plagiochins A and D, Macrocyclic Bis(bibenzyls), by Pd(0) Catalyzed Intramolecular Stille-Kelly Reaction1
Yoshiyasu Fukuyama,* Hideyuki Yaso, Takashi Mori, Hironobu Takahashi, Hiroyuki Minami, and Mitsuaki Kodama
*Faculty of Pharmaceutical Sciences, Tokushima Bunri University, 180 Nishihamabouji, Yamashiro-machi, Tokushima, 770-8514, Japan
Abstract
Total syntheses of plagiochins A (1) and D (4), the former of which exhibits a significant neurotrophic activity, have been accomplished. The key 16-membered ring closure in 4 has been achieved directly from the dibromoperrottetin derivative (7) by Pd(0) catalyzed intramolecular Stille-Kelly reaction, whereas 1 has been synthesized from the dibromide (28) via the trimethylstannyl compounds (29) and (30) by Pd(0) catalyzed intramolecular Stille reaction.
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■ Azepine and [1,3]Oxazepine Fused Ring Construction through a Cationic Cyclization: an N-acyliminium Ion Trapping of an Oxygen Atom or Olefin
Aïcha Mamouni, Adam Daïch, Stefan Marchalin, and Bernard Decroix
*Laboratoire de Chimie, URCOM, Faculté des Sciences et Techniques, Université du Havre, 25 Rue Philippe Lebon, B.P. 540 76058 Le Havre Cedex, France
Abstract
Carbophilic addition on (and/or sodium borohydride reduction of) an imide ester functionality (3) proceeds with extremely high regioselectivety to produce bifunctionalized hydroxy-ω-carbinol lactam products (4) and (8). These species could act as N-acyliminium ion precursors and, via an O-cationic or π-cationic cyclization, and they led regioselectively in high yields to fused triheterocyclic azepine (11) or [1,3]oxazepine (18).
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■ A Convenient Determination of Chiral Pteridines; Application of Fluorescence Detected Circular Dichroism (FDCD) to the Major Pterin from Escherichia coli
Takashi Sugimoto,* Kazuhisa Ikemoto, Shizuaki Murata, Masahiro Tazawa, Takahide Nomura, Yasumichi Hagino, Hiroshi Ichinose, Toshiharu Nagatsu, and Akio Wada
*Graduate School of Human Informatics, Nagoya University, Nagoya 464-8601, Japan
Abstract
The major pterin from Escherichia coli was determined as L-monapterin, by applying fluorescence detected circular dichroism (FDCD). FDCD was highly sensitive and specific to fluorescent chiral pterin, and allowed structure determination even in the presence of non-fluorescent contaminants.
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■ 1,3-Dipolar Cycloadditions of 3-Bromo-1,5- and 3-Bromo-1,7-azulenequinones with Diazomethane, Diphenylnitrilimine, and Benzonitrile Oxide
Yong Zhe Yan, Katsuji Hirowatari, Kanji Kubo, Nobuo Kato, Akira Mori,* Hitoshi Takeshita,1 and Tetsuo Nozoe
*Instituete of Advanced Material Study, Kyushu University, 6-1, Kasuga-koen, Kasuga 816-8580, Japan
Abstract
The reactions of 3-bromo-1,5- and 3-bromo-1,7-azulenequinones with diazomethane gave cyclooctatrienone derivatives and a [4+2] 1,3-dipolar adduct while they reacted with diphenylnitrilimine and benzonitrile oxide to give the corresponding [4+2] 1,3-dipolar adducts, showing the different site selectivities. 3-Bromo-1,5-azulenequinone reacted with the 1,3-dipoles dominantly to form the adducts on the cyclopentenone part while 3-bromo-1,7-azulenequinone reacted on the seven-membered ring.
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■ Xanthate Mediated Generation of the Benzotriazol-1-yl-methyl Radical and Its Subsequent Addition to a Variety of Olefins
Alan R. Katritzky,* Martin A. C. Button, and Sergey N. Denisenko
*Center for Heterocyclic Compounds, Department of Chemistry, University of Florida, Gainesville, FL 32611-7200, U.S.A.
Abstract
The first generation of the benzotriazol-1-ylmethyl radical (3) is reported from S-(1H-1,2,3-benzotriazol-1-ylmethyl)-O-ethylcarbonodithioate (1). Subsequent additions of radical (3) to a variety of olefins are demonstrated.
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■ Preparation of β-Substituted γ-Keto Esters by the Grignard Reaction on N-Acylpyrazoles
Choji Kashima,* Yoshie Shirahata, and Yoshihiro Tsukamoto
*Department of Chemistry, University of Tsukuba, Ten-nodai, Tsukuba-shi, Ibaraki, 305-8571, Japan
Abstract
Various γ-keto esters were prepared by either the alcoholysis of N-(4-oxoalkanoyl)pyrazoles or the Grignard replacement of pyrazole moiety of 4-(N-pyrazolyl)-4-oxoalkanoic esters. By using 3-phenyl-l-menthopyrazole as a chiral auxiliary, β-substituted γ-keto esters were enantioselectively obtained.
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■ Revision of the Structure of a New Coumarin Isolated from Artemisia carviforia Wall
Takashi Harayama,* Keiko Katsuno, Yoshitaka Nishita, Masako Fujii, Hitoshi Abe, and Yasuo Takeuchi
*Faculty of Pharmaceutical Science, Okayama University, 1-1-1 Tsushima-naka, Okayama 700-8530, Japan
Abstract
Four coumarins (1-4) were synthesized by the routes shown in Schemes 2-5, respectively. The previously proposed structure for a new coumarin isolated from Artemisia carviforia was incorrect; the structure of the coumarin is represented by formula (3).
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■ Reductive Cyclization of 8-(2-Nitrophenyl)-1-azaazulene Derivatives; Formation of 6a,7-Diazanaphth[3,2,1-cd]azulene and 7H-1,7-Diazaindeno[1,2-e]azulene Systems, a New DNA Intercalater
Noritaka Abe,* Maki Nabeshima, Hiroyuki Fujii, Akikazu Kakehi, Yuichi Kageura, and Takeo Konakahara
*Department of Chemistry, Faculty of Science, Yamaguchi University, Yamaguchi 753-8512, Japan
Abstract
Reaction of ethyl 2-dimethylamino-8-(2-nitrophenyl)-1-azaazulene-3-carboxylate with hexamethylphosphorous triamide gave ethyl 6-dimethylamino-6a,7-diazanaphth[3,2,1-cd]azulene-5-carboxylate (7b) and ethyl 2-dimethylamino-7H-1,7-diazaindeno[1,2-e]azulene-3-carboxylate (8b). The structures of 7b and 8b were determined by X-Ray structure analyses. Compound (8b) was intercalated to Calf-Thymus DNA and a 12-mer DNA with binding constants KD = 1.55 x 106 and 1.75 x 106 M-1, respectively.
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■ Diastereoselective Addition of Organometallic Reagents to (R)-2,3-Isopropylidenedioxy-1-(2-furyl)-1-propanone Yielding Chiral Tertiary Furyl Carbinols
Masayoshi Tsubuki,* Naohiro Tarumoto, and Toshio Honda*
*Faculty of Pharmaceutical Sciences, Hoshi University, 2-4-41 Ebara, Shinagawa-ku, Tokyo 142-8501, Japan
Abstract
The nucleophilic addition of either organolithium or Grignard reagents to (R)-2,3-isopropylidenedioxy-1-(2-furyl)-1-propanone (1) in Et2O afforded the corresponding anti isomers predominantly, whereas addition of organolithium reagents in THF with HMPA as a co-solvent gave the syn isomers in moderate selectivities.
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■ Synthesis and Mercurophilic Properties of Acyclic and Thiolariat Ethers Having a Tropone Pendant
Kanji Kubo* and Akira Mori*
*Instituete of Advanced Material Study, Kyushu University, 6-1, Kasuga-koen, Kasuga 816-8580, Japan
Abstract
Acyclic and thiolariat ether derivatives (3 and 4) having a tropone pendant were synthesized. Acyclic and thiolariat ether (3, 4a and 4b) were used as carriers for transport of Hg2+ through a chloroform liquid membrane. Thiolariat (4c) did not transport from source phase to receiving phase of Hg2+, but extracted into chloroform layer. Effective Hg2+ extractability of 4c was a result of the synergistic coordination of oxygen and sulfur atoms of the thiolariat ether.
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■ Quinolone Analogues 3. Synthesis of 1,3-Dialkyl-4-oxo-1,4-dihydropyridazino[3,4-b]quinoxalines
Yoshihisa Kurasawa,* Shinichi Ohshima, Yaeko Kishimoto, Miharu Ogura, Yoshihisa Okamoto, and Ho Sik Kim
*School of Pharmaceutical Sciences, Kitasato University, Shirokane, Minato-ku, Tokyo 108-8641, Japan
Abstract
The 1-alkyl-3-methyl-4-oxo-1,4-dihydropyridazino[3,4-b]quinoxalines (10a-d) were synthesized from the quinoxaline N-oxides (8a-d) via the oxidation of the 4-acetyl-1-alkyl-3-methyl-1,5-dihydropyridazino[3,4-b]quinoxalines (9a-d) with N-bromosuccinimide/water, sodium bromate, or selenium dioxide, while the 1-alkyl-3-ethyl-4-oxo-1,4-dihydropyridazino[3,4-b]quinoxalines (13a-d) were synthesized from the quinoxaline N-oxides (8a-d) via the oxidative ring transformation of the 1-alkyl-3-ethyl-2,3-dihydro-4-hydroxy-1H-1,2-diazepino[3,4-b]quinoxalines (12a-d), respectively.
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■ Preparation, Structure, and Properties of 1,3-Bis(1,4-dithiafulven-6-yl)azulenes
Akira Ohta,* Kyoko Yamaguchi, Naoki Fujisawa, Yoshiro Yamashita, and Kunihide Fujimori*
*Department of Chemistry, Faculty of Science, Shinshu University, Asahi, Matsumoto 390-8621, Japan
Abstract
Novel bis(1,3-dithiole) donors containing an azulene spacer unit have been prepared from 1,3-diformylazulene using a Wittig—Horner reaction. The cyclic voltammetry revealed that they are stronger electron donors than tetrathiafulvalene and show amphoteric characters. The structural features of a benzo-fused derivative were investigated by an X-Ray analysis. The spectroelectro-chemical studies on the methylthio derivative revealed that the cation radical and dication state show the longest absorption maxima at 612 and 721 nm, respectively.
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■ Generation and Amphoteric Redox Properties of Novel Neutral Radicals with the TTF-TCNQ Hybrid Structure1
Takanori Suzuki,* Masahiro Yamada, Masakazu Ohkita, and Takashi Tsuji
*Division of Chemistry, Graduate School of Science, Hokkaido University, Sapporo 060-0810, Japan
Abstract
One electron oxidation of 4-(2-tetrathiafulvalenyl)phenyl substituted dicyanomethylides (1-) gave black solids of the title radicals (1·). They exhibit quite high electrochemical amphotericity, which may be responsible for their good electrical conductivities (σ = ca. 10-7 S cm-1) as a single component. Isomeric radicals (2·) with a m-phenylene spacer could not be obtained under the similar conditions probably due to insufficient delocalization of the unpaired electron.
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■ Lewis Acid Catalysis of Second-Generation Metallosalen Complexes: an Explanation for Stereochemistry of Asymmetric Hetero Diels-Alder Reaction
Jun Mihara, Kohsuke Aikawa, Tatsuya Uchida, Ryo Irie, and Tsutomu Katsuki*
*Department of Chemistry, Faculty of Science, Graduate School, Kyushu University, 6-10-1 Hakozaki, Higashi-ku, Fukuoka 812-8581, Japan
Abstract
Chloro nitrosyl (R,S)-(salen)ruthenium(II) complex served as a good catalyst for asymmetric hetero Diels-Alder (HDA) reaction of Danishefsky's diene with a wide variety of aldehydes. In contrast with this, (R,R)-(salen)-chromium(III) and -manganese(III) complexes well catalyze HDA reaction of simple aldehydes, while (R,S)-(salen)-chromium(III) and -manganese(III) complexes better catalyze HDA reaction of aldehydes bearing a precoordinating group. These features of metallosalen-catalyzed HDA reactions were rationalized by assuming that HDA reaction of aldehydes bearing a precoordinating group would proceed through aldehyde-metallosalen complex which takes cis-β-structure.
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■ Optical Resolution of 2-azabicyclo[2.2.1]hept-5-en-3-one by Inclusion Complexation with Brucine
Koichi Tanaka, Masako Kato, and Fumio Toda*
*Department of Chemistry, Faculty of Science, Okayama University of Science, 1-1 Ridai-cho, Okayama 700-0005, Japan
Abstract
A simple optical resolution method of 2-azabicyclo[2.2.1]hept-5-en-3-one by inclusion complexation with brucine was reported. The crystal structure of the inclusion complex was analyzed by X-Ray diffraction in order to elucidate the mechanism of the efficient chiral recognition in the inclusion crystals.
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■ Synthesis of New Chiral Catalysts, 2-Azanorbornyloxazolidines, for Enantioselective Addition of Diethylzinc to Aldehydes
Hiroto Nakano,* Yuko Okuyama, Kazuto Iwasa, and Hiroshi Hongo*
*Tohoku Pharmaceutical University, Aoba-ku, Sendai 981-8558, Japan
Abstract
Optically active 2-azanorbornyloxazolidines were prepared from 2-azanorbornylmethanols and catalyzed the enantioselective addition of diethylzinc to aldehydes to give optically active secondary alcohols.
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■ Synthesis of 2,5-Disubstituted Tetrahydrofurans Catalyzed by Palladium(0)
Osamu Hara,* Kazushige Fujii, Yasumasa Hamada, and Youji Sakagami
*Faculty of Pharmaceutical Sciences, Chiba University, Inage-ku, Chiba 263-8522, Japan
Abstract
A stereoselective cyclization of an allylic ester to 2,5-disubstituted tetrahydrofurans catalyzed by palladium(0) is demonstrated. In this cyclization, acetoxy heptenol (6a) having a free hydroxy group prefered trans isomer to cis isomer. By the use of the protected acetoxy heptenol (6b), the cis selectivity was observed. The stereoselectivity was enhanced by the use of DPPIO ligand.
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■ Syntheses of Wasabi Phytoalexin (Methyl 1-Methoxyindole-3-carboxylate) and Its 5-Iodo Derivative, and Their Nucleophilic Substitution Reactions1
Masanori Somei,* Asuka Tanimoto, Hitomi Orita, Fumio Yamada, and Toshiharu Ohta
*Faculty of Pharmaceutical Sciences, Kanazawa University, 13-1 Takara-machi, Kanazawa 920-0934, Japan
Abstract
A simple synthetic method for methyl 1-methoxyindole-3-carboxylate, a phytoalexin isolated from Wasabia japonica, syn. Eutrema wasabi, and its 5-iodo derivative is reported. They underwent nucleophilic substitution reactions selectively at the 2-position.
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■ Alternative Synthesis of B/C-cis Hexahydrobenzo[c]phenanthridine from 2-Phenyl-1-tetralone
Makoto Yoshida, Toshiko Watanabe, and Tsutomu Ishikawa*
*Faculty of Pharmaceutical Sciences, Chiba University, 1-33 Yayoi-cho, Inage-ku, Chiba 263-8522, Japan
Abstract
A B/C-cis hexahydrobenzo[c]phenanthridine (7) was alternatively prepared by the hydride-reduction of a tetrahydrobenzo[c]phenanthridine derivative (6) under acidic condition, which was derived from 2-phenyl-1-tetralone oxime (3) through four steps (reductive amidation, methylation, Bischler-Napieralski cyclization, and hydride reduction).
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■ Triphosgene: a Versatile Reagent for Bischler-Napieralski Reaction
Tatsuru Saito, Makoto Yoshida, and Tsutomu Ishikawa*
*Faculty of Pharmaceutical Sciences, Chiba University, 1-33 Yayoi-cho, Inage-ku, Chiba 263-8522, Japan
Abstract
Triphosgene causes direct formation of quaternary benzo[c]phenanthridines such as anti-tumor active nitidine (2a) chloride by Bischler-Napieralski reaction of 2-phenyl-1-(N-methylformamido)naphthalenes under heating in acetonitrile.
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■ Preparation of Azulenequinones Containing Azacrown Moieties and the Singular Complexation of Sodium or Potassium Cation by 3,5-Bis(aza-18-crown-6)-1,7-azulenequinone in Solution
Ohki Sato, Noriko Matsuda, and Josuke Tsunetsugu*
*Department of Chemistry, Faculty of Science, Saitama University, Saitama, Saitama 338-8570, Japan
Abstract
Efficient syntheses of azulenequinones containing azacrown ether moieties as pendants (2)–(5) were carried out. The singular complexation properties of 3,5-bis(aza-18-crown-6)-1,7-azulenequinone (5b) with sodium or potassium cation were investigated by 1H NMR measurement.
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■ Nucleophilic Aromatic Substitution of Hydrogen as a Tool for the Synthesis of Indole and Quinoline Derivatives
Mieczyslaw Makosza* and Krzysztof Wojciechowski
*Institute of Organic Chemistry, Polish Academy of Sciences, ul. Kasprzaka 44/52, PL-01-224 Warszawa 42, P.O.Box 58, Poland
Abstract
Indole and quinoline belong to the most important heterocyclic systems. Although there are numerous methods of syntheses of these heterocycles, new processes leading to these systems have still attracted considerable attention. Nucleophilic Aromatic Substitution of Hydrogen in nitroarenes and other electrophilic arenes opens new rich possibilities for synthesis of indole and quinoline derivatives. In this review a variety of methods for synthesis of these heterocycles based on the initial nucleophilic substitution of hydrogen are discussed.
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■ Photochemical Dimerization in Solution of Heterocyclic Substituted Alkenes Bearing an Electron Withdrawing Group
Maurizio D'Auria
*Dipartamento di Chimica, Università della Basilicata, Via N. Sauro 85, 85100 Potenza, Italy
Abstract
The photochemical dimerization in solution of heterocycle substituted alkenes bearing electron withdrawing groups is reported. The reactions occurred both in the singlet and in the triplet states showing good regio- and stereoselectivities. The regioselectivity can be explained assuming that the dimerization reaction is frontier orbitals controlled. The stereoselectivity can be explained assuming the formation of the most stable isomers
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■ The Structural Aspects of Carbapenem Antibiotics
Makoto Sunagawa* and Akira Sasaki
*Sumitomo Pharmaceuticals Research Center, 1-98, Kasugadenaka 3-chome, Konohana-ku, Osaka 554-0022, Japan
Abstract
The discovery of thienamycin in 1976 caused much synthetic research effort to be concentrated on carbapenem antibiotics, by many groups. To date, two carbapenems, which need to be coadministered with other drugs, and then a new generation carbapenem, which could be utilized as a single agent, were developed for clinical use based on the progress of synthetic chemistry. Today, attention has been focused on the development of next generation carbapenem antibiotics. These trends of the carbapenem antibiotics developed in last quarter century are reviewed from a viewpoint of their chemical structures.
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■ Biotransformation of Terpenoids from the Crude Drugs and Animal Origin by Microorganisms
Toshihiro Hashimoto, Yoshiaki Noma, and Yoshinori Asakawa*
*Faculty of Pharmaceutical Sciences, Tokushima Bunri University, Yamashiro-machi, Tokushima, 770-8514, Japan
Abstract
Terpenoids, dehydrocostuslactone (2), costunolide (3), α-, β-, and γ-cyclocostunolides (4~6), α-santonin (7) and atractylon (8) isolated from the crude drugs and (-)-ambrox (9) from animal origin were biotransformed by Aspergillus niger, A. cellulosae, and Botryospaeria dothidea etc. to afford the structurally interesting metabolites. Their stereostructures were established by a combination of high-resolution NMR spectrum, X-Ray crystallographic analysis and chemical reaction. The metabolic pathways of terpenoids by A. niger resembled those by mammals, but are quite different from those by A. cellulosae.