Regular Issue

Vol. 36, No. 1, 1993

23 data found. 1 - 23 listed
Communication | Regular issue | Vol 36, No. 1, 1993, pp. 1 - 6
Published online:
DOI: 10.3987/COM-92-6138
1,2,3,4-Tetrahydro-1,6-naphthyridines. Part 2. Formation and Unexpected Reactions of 1,2,3,4-Tetrahydro-7H-pyrano[4,3-b]pyridine-2,7-diones

Pedro J. Victory,* Jordi Teixidó, José I. Borrell, and Núria Busquets

*CETS Institut Químic de Sarriá, Universitat Ramon Llull, Departament de Química Organica, Via Augusta 390, E-08017 Barcelona, Spain


The nucleophilic substitution of the enol methoxy group of pyridones (1) by methyl cyanoacetate led to (Z)-5-cyano-6-cyanomethoxycarbonylmethylenepiperidones (6), which underwent cyclization in acid medium to 1,2,3,4-tetrahydro-7H-pyrano[4,3-b]pyridine-2,7-diones (7). Surprisingly, the treatment of 7 with ammonia yielded the 5-cyano-6-cyanomethyl substituted pyridones (11) which were not accessible by reaction of 1 with NaCH2CN.

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Communication | Regular issue | Vol 36, No. 1, 1993, pp. 7 - 11
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DOI: 10.3987/COM-92-6176
The Tandem Beckmann and Huisgen-White Rearrangement as an Alternative to the Baeyer-Villiger Oxidation of the 9-Azabicyclo[3.3.1]nonan-3-one System: A Facile Route to (±)-Dihydropalustramic Acid

Takefumi Momose,* Kazuhito Okumura, Hisayuki Tsujimori, Kaori Inokawa, Genzoh Tanabe, Osamu Muraoka,* Yoh Sasaki, and Conrad Hans Eugster

*Faculty of Pharmaceutical Sciences, Kinki University, 3-4-1, Kowakae, Higashi-Osaka 577-8502, Japan


The transformation of the "fork head ketone" (1) into the corresponding bicyclic lactone (4) via the Beckmann followed by the Huisgen-White Rearrangement is described. An α-ethyl-substituted bicyclic ketone (5) was converted efficiently to dihydropalustramic acid (6), a degradation product from the alkaloid palustrine.

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Communication | Regular issue | Vol 36, No. 1, 1993, pp. 13 - 20
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DOI: 10.3987/COM-92-6177
Studies with Plant Cell Culture of Podophyllum peltatum L. II. Biotransformation of Dibenzylbutanolides to Lignans. Development of a "Biological Factory" for Lignan Synthesis

James P. Kutney,* Yung Ping Chen, Shixiang Gao, Gary M. Hewitt, Francisco Kuri-Brena, Radka K. Milanova, and Nikolay M. Stoynov

*Department of Chemistry, University of British Columbia, 2036 Main Mall, Vancouver, B.C. V6T 1Z1, Canada


An efficient and versatile synthetic route to appropriate dibenzylbutanolides suitable for biotransformation to lignans as potentila intermediates for the syntheses of the clinical anti-cancer drug etoposide has been developed. Biotransformation of such substrates, for example 10, with cell cultures of Podophyllum peltatum affords a potentially exciting route to this drug. Of particular significance is the development of a semi-continuous fermentation process with these plant cells wherein successive additions of substrate and isolation of end products can be pursued with a given batch of cells and over a period of several months. Biotransformation times for the conversion of 10 to 11 and 12 are short (usually 24-48 h). Although conditions have not yet optimized, this "biological factory" for lignan synthesis provides a novel approach for the use of plant cells, in combination with chemistry, for continuous and large scale production of such metabolites.

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Communication | Regular issue | Vol 36, No. 1, 1993, pp. 21 - 24
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DOI: 10.3987/COM-92-6182
1,3-Dipolar Cycloaddition Reactions of N-Aryl-2,4,6-cycloheptarien-1-imines with p-Substituted Benzonitrile Oxides: Formations of 1,2,4-Oxadiazaspiro[4.6]undeca-6,8,10-trienes

Kazuaki Ito, Katsuhiro Saito,* and Kensuke Takahashi

*Department of Applied Chemistry, Nagoya Institute of Technology, Gokiso-cho, Showa-ku, Nagoya 466-8555, Japan


Reactions of N-aryl-2,4,6-cycloheptatrien-1-imines with p-substituted benzonitrile oxides afforded 1,2,4-oxadiazaspiro[4.6]undeca-6,8,10-trienes via [2+4] type cycloadditions. The study of substituent effects on the reaction rates suggested the nucleophilic attacks of the imines to the nitrile oxides.

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Communication | Regular issue | Vol 36, No. 1, 1993, pp. 25 - 28
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DOI: 10.3987/COM-92-6183
Mechanistic Investigation of an Intramolecular Rearrangement in a Heterocyclic Allyloxy Iminium Compound

Claude Agami,* François Couty, and Jing Lin

*Laboratoire de Chimie Organique Associé au CNRS, Université P. et M. Curie, Boîte 181, 4 place Jussieu, 75005 Paris, France


A new rearrangement involving an ene iminium system derived from a homochiral 2-allyloxy-3-phenylthiomorpholine is reported.

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Communication | Regular issue | Vol 36, No. 1, 1993, pp. 29 - 32
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DOI: 10.3987/COM-92-6185
Directed Lithiation of 1-Triisopropylsilylgramine. A Short Access to 3,4-Disubstituted Indoles

Masatomo Iwao

*Department of Chemistry, Faculty of Liberal Arts, Nagasaki University, 1-14, Bunkyo-machi, Nagasaki 852-8521, Japan


1-Triisopropylsilylgramine was lithiated regioselectively at C-4 by treatment with t-BuLi in ether at 0 °C for 1 h. The lithiated species was trapped with a variety of electrophiles to furnish 4-functionalized gramine derivatives in good yields. Replacement of the triisopropylsilyl protecting group by a methyl group resulted in C-2 selective lithiation under the similar reaction conditions.

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Communication | Regular issue | Vol 36, No. 1, 1993, pp. 33 - 36
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DOI: 10.3987/COM-92-6205
On the Regioselectivity in the Hurd-Mori Reaction

Mikako Fujita, Takeo Kobori,* Tamejiro Hiyama, and Kiyoshi Kondo

*Sagami Central Research Center, 4-4-1 Nishi-Ohnuma, Sagamihara, Kanagawa 229-0012, Japan


Various α-substituted (Y) acetone hydrazones were subjected to the Hurd-Mori reaction to give the 4-methyl-5-Y-substituted 1,2,3-thiadiazoles and/ or 4-Y-CH2 derivatives. The ratio of the two products changed drastically depending on the kind of the substituent Y and was parallel to the relative rate of enolization of the two α-carbons in the parent ketones.

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Communication | Regular issue | Vol 36, No. 1, 1993, pp. 37 - 40
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DOI: 10.3987/COM-92-6213
Stereoselective Synthesis of Optically Active E- and Z-Homoallyl Alcohols from Epoxides

Kentaro Okuma,* Yuichiro Tanaka, Hiroshi Ohta, and Haruo Matsuyama

*Department of Chemistry, Faculty of Sciences, Fukuoka University, 8-19-1 Nanakuma, Jonan-ku, Fukuoka 814-0180, Japan


Optically active E- and Z-homoallyl alcohols were prepared by Wittig and Warren olefination starting from optically active 3-hydroxyalkyltriphenylphosphonium salts, which were obtained by the reaction of epoxides with methylenetriphenylphosphorane and dibenzoyltartric acid followed by optical resolution.

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Communication | Regular issue | Vol 36, No. 1, 1993, pp. 41 - 44
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DOI: 10.3987/COM-92-9216
Acalycigorgins A, B, and C, Three New Biologically Active Diterpenoids from the Gorgonian Acalycigorgia Sp.

Masamitsu Ochi,* Kumi Kataoka, Akira Tatsukawa, Hiyoshizo Kotsuki, and Kozo Shibata*

*Faculty of Science, Kochi University, 2-5-1, Akebono-cho, Kochi 780-8520, Japan


Three new biologically active diterpenoids, acalycigorgins A, B, and C, have been isolated form the gorgonian Acalycigorgia sp. and their structures were fully characterized by extensive 2D-nmr studies.

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Paper | Regular issue | Vol 36, No. 1, 1993, pp. 45 - 54
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DOI: 10.3987/COM-92-6028
Synthesis and SRN1 Reaction of the First Quinone-Oxazole Bioreductive Alkylating Agent

Michel P. Crozet,* Jean-François Sabuco, Isabelle Tamburlin, Michel Barreau, Luc Giraud, and Patrice Vanelle

*Radicaux Libres et Synthèse, CNRS URA 1412, Faculté des Sciences et Techniques de Saint-Jérôme, P.O. Box 562, Université de Droit, d’Economie et des Sciences d’Aix-Marseille, 13397 Marseille Cedex 13, France


2-(2-Chloromethyloxazol-5-yl)-3,5,6-trimethyl-1,4-benzoquinone, the first compound of a new quinone-heterocyclic class of bioreductive alkylating agent, was prepared from trimethylhydroquinone in 8 steps and reacted by SRN1 reaction with lithium salt of 2-nitropropane. The C-alkylation derivative showing its ability to react as one electron bioreductive alkylating agent was obtained in 88% yield.

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Paper | Regular issue | Vol 36, No. 1, 1993, pp. 55 - 62
Published online:
DOI: 10.3987/COM-92-6104
Nucleophilicity of 3-Alkyl-2-(N-cyanoimino)thiazolidines: Methylated Products and Their Reactivity

Chuzo Iwata,* Tetsuya Kawakami, Michitaro Fujimoto, Yumi Nakamoto, and Tetsuaki Tanaka

*Faculty of Pharmaceutical Sciences, Osaka University, 1-6 Yamadaoka, Toyonaka, Osaka 560-0043, Japan


3-Alkyl-2-(N-cyanoimino)thiazolidines were methylated mainly at the nitrile nitrogen atom with trimethyloxonium tetrafluoroborate (Me3O·BF4). The reaction of the methylated products, the nitrilium salts, with sodio diethyl malonate was described.

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Paper | Regular issue | Vol 36, No. 1, 1993, pp. 63 - 69
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DOI: 10.3987/COM-92-6115
Pyrrolo[2,1-c][1,4]benzodiazepines: Synthesis of N-Substituted Amidines

Marie-Paule Foloppe, Isabelle Rault, Sylvain Rault, and Max Robba*

*Laboratorie de Chimie Thérapeutique, U.E.R. des Sciences Pharmaceutiques, 1, rue Vaubénard, 14032 Caen Cedex, France


Synthesis of N-substituted amidines derived from pyrrolo[2,1-c][1,4]benzodiazepines is described

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Paper | Regular issue | Vol 36, No. 1, 1993, pp. 71 - 78
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DOI: 10.3987/COM-92-6141
Photoreaction of 1- and 3-Aralkyl Alicyclic Thioimides: Facile Syntheses of Various Azabicycloalkanes via Norrish Type II Process

Kazuaki Oda,* Yuichi Fukuzawa, Kosei Ohno, Minoru Machida, and Yuichi Kanaoka

*Faculty of Pharmaceutical Scicences, Higashi-Nippon-Gakuen University, 1757 Kanazawa, Toubetu-cho, Ishikari-gun, Hokkaodo 061-0212, Japan


Photolysis of the 1-(ω-aralkyl)cyclic thioimides (1b,e,g,h) gave a pair of stereoisomers of 1-azabicycloalkanes (2, 3) in moderate yields. Similarly, in 3-(ω-phenylalkyl)cyclic thioimides (5a-e), a pair of stereoisomers of 2-azabicycloalkanes (6, 7) were obtained.

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Paper | Regular issue | Vol 36, No. 1, 1993, pp. 79 - 86
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DOI: 10.3987/COM-92-6148
Thiaphysovenol Phenylcarbamates: X-Ray Structures of Biologically Active and Inactive Anticholinesterase Agents

Judith L. Flippen-Anderson, Xiao-shu He, Arnold Brossi,* Nigel H. Greig, and Stanley I. Rapoport

*Laboratory of Analytical Chemistry, NIDDK, National Institute of Health, Bethesda, MD 20892, U.S.A.


The X-ray structure of the biologically active phenylcarbamate (4), and the biologically inactive phenylcarbamate (5) of the thiaphysovenol series, reveal that the two aromatic ring systems are differently oriented towards each other. The abolute configuration of both compounds, determined by using the anomolous scattering from the sulfur atoms, was found to be (3aS-cis).

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Paper | Regular issue | Vol 36, No. 1, 1993, pp. 87 - 99
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DOI: 10.3987/COM-92-6166
8H-Pyrazolo[5’,1’:2,3]pyrimido[5,4-d][1,2]diazepine: A New Tricyclic System

Fabrizio Bruni,* Barbara Cosimelli, Annarella Costanzo, Gabriella Guerrini, and Silvia Selleri

*Università di Firenze, Dipartimento di Scienze Farmaceutiche, Via Gino Capponi 9, I-50121 Firenze, Italy


Starting from a series of 6-acetyl-7-(2-dimethylaminovinyl)pyrazolo[1,5-a]pyrimidines (2a-g), several derivatives of the pyrazolo[5’,1’: 2,3]pyrimido[5,4-a][1,2]diazepine system (3a-g) were obtained by reaction with hydrazine hydrate. Some compounds were finally alkylated at N-8 position.

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Paper | Regular issue | Vol 36, No. 1, 1993, pp. 101 - 105
Published online:
DOI: 10.3987/COM-92-6168
The Synthesis of Three Isomers of the Food Carcinogen IQ

Erik Ronne and Spiros Grivas*

*Department of Chemistry, Swedish University of Agricultural Sciences, P.O.Box 7015, SE-750 07 Uppsala, Sweden


2-Amino-3-methyl-3H-imidazo[4,5-h]quinoline, 2-amino-3-methyl-3H-imidazo[4,5-f]isoquinoline and 2-amino-3-methyl-3H-imidazo[4,5-h]isoquinoline were synthesized from 7-methoxyquinoline, 6- and 7-methoxyisoquinolines in 21-28% overall yields.

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Paper | Regular issue | Vol 36, No. 1, 1993, pp. 107 - 116
Published online:
DOI: 10.3987/COM-92-6186
Stereochemistry of Berbine and Some Related Compounds

Georges Memetzidis, Louis Jung, and Jean-Francois Stambach*

*Laboratoire de Chimie Thérapeutique, U.F.R. des Sciences Pharmaceutiques, Université Louis Pasteur, 74, route du Rhin, BP 24, 67401 ILLKIRCH Cedex, France


The stereochemistry of berbines (1-15) and their berbane (16) and berbinanes (17 and 18) derivatives was established on the basis of their ir, 1H-nmr, 13C-nmr spectral data and the rates of methiodide formation. All the compounds in this study were found to have a trans-B/C conformation whereas berbinane (18) had a cis-A/B configuration.

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Paper | Regular issue | Vol 36, No. 1, 1993, pp. 117 - 121
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DOI: 10.3987/COM-92-6187
Characterization of Lariciresinol Glucosides from Osmanthus asiaticus

Masataka Sugiyama and Masao Kikuchi*

*Department of 2nd Analytical Chemistry, Tohoku College of Pharmacy, 4-4-1 Komatsushima, Aoba-ku, Sendai 981-8558, Japan


Two lariciresinol glucosides, lariciresinol-4’-O-β-D-glucoside (1) and lariciresinol-4-O-β-D-glucoside (2), were isolated from the bark of Osmanthus asiaticus and the 1H- and 13C-nmr assignments were made by using nOe and 2D-nmr techniques.

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Paper | Regular issue | Vol 36, No. 1, 1993, pp. 123 - 132
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DOI: 10.3987/COM-92-6191
Intramolecular Diels-Alder Reaction of 3-Formimidoylindoles: Synthesis of Fused Pyridoindole Compounds

Yasuo Shimoji,* Toshihiko Hashimoto, Yoji Furukawa, and Hiroaki Yanagisawa

*Sankyo Research Laboratories, Sankyo Co., Ltd., 1-2-58 Hiromachi, Shinagawa-ku, Tokyo 140-8710, Japan


Intramolecular Diels-Alder reaction of 3-formimidoylindoles having olefinic substituents at the 1-position of the indole ring gave stereoselectively fused pyridoindole compounds. Double bond migration from 2,3,3a,4,12,12a,12b,12c-octahydrobenz[de]indolo[3,2,1-ij][1,6]naphthyridin-11(1H)-ones (4) to 2,3,3a,4,5,12,12a,12b-octahydrobenz[de]indolo[3,2,1-ij][1,6]naphthyridin-11(1H)-one (5) was performed using 10% Pd-C as a catalyst.

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Paper | Regular issue | Vol 36, No. 1, 1993, pp. 133 - 144
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DOI: 10.3987/COM-92-6193
An Efficient and Novel Synthesis of Fused Thiazol-2(3H)-ones

Baldev Singh,* Patrick O. Pennock, George Y. Lesher, Edward R. Bacon, and Donald F. Page

*Department of Medical Chemistry, Sterling Winthrop Pharmaceuticals Research Division, 81 Columbia Turnpike, Rensselaer, NY 12144, U.S.A.


Reaction of o-bromo aromatic amines (2, 4, 7, 10, 15) with ethyl potassium xanthate gave the corresponding fuesd thiazol-2(3H)-thiones (16, 19, 22) which in turn were first alkylated with methyl iodide and then treated with sodium methoxide to produce fused thiazol-2(3H)-ones (18, 21, 24). Treatement of 4-(4-pyridinyl)benzenamine dihydrobromide (1) with DMSO gave 2-bromo-4-(4-pyridinyl)benzenamie (2). Reduction of 4-(4-bromo-3-nitrophenyl)pyridine (3) with stannous chloride gave 2-bromo-5-(4-pyridinyl)benzenamine (4). Treatment of 5-bromo-2-methyl[3,4’-bipyridin]-6(1H)-one (5) with phosphorous oxychloride and ammonia sequentially yielded amino compound (7). Hofmann reaction of 2-chloro-6-methyl[3,4’-bipyridine]-3-carboxamide resulted in amino compound (10). 5-Acyl-6-methylpyridin-2(1H)-ones (11) were converted to 3-bromo-1,6-naphthyridin-2-amines (15) via a four-step sequence.

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Paper | Regular issue | Vol 36, No. 1, 1993, pp. 145 - 148
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DOI: 10.3987/COM-92-6195
Convenient and Practical Synthesis of 5-Chloro-4-hydroxy-2(1H)-pyridinone

Shin-go Yano, Tomoyasu Ohno, and Kazuo Ogawa*

*Hanno Research Center, Taiho Pharmaceutical Co. Ltd., 1-27 Misugidai, Hanno, Saitama 357-0041, Japan


5-Chloro-4-hydroxy-2(1H)-pyridinone (1) was prepared by 4-step reactions via the key intermediate 5-chloro-3-cyano-4-methoxy-2(1H)-pyridinone (5). This synthetic route has several advantages over the reported methods in procedure, yield and applicability.

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Paper | Regular issue | Vol 36, No. 1, 1993, pp. 149 - 155
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DOI: 10.3987/COM-92-6206
Synthesis of a Useful Chiral Building Block, (S)-5-Acetoxy-2-penten-4-olide from D-Glucose

Ichiro Honda, Makoto Shibagaki,* Koshi Koseki, Hideyuki Kuno, Kyoko Takahashi, and Hajime Matsushita

*Life Science Research Laboratory, Japan Tobacco Inc., 6-2, Umegaoka, Midori-ku, Yokohama, Kanagawa 227-8512, Japan


A new method for preparation of (S)-5-acetoxy-2-penten-4-olide starting from D-glucose with 5 steps is described

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Review | Regular issue | Vol 36, No. 1, 1993, pp. 157 - 189
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DOI: 10.3987/REV-92-451
Novel Pyridodiindoles, Azadiindoles, and Indolopyridoimidazoles via the Fischer-Indole Cyclization

Michael J. Martin, Linda J. Dorn, and James M. Cook*

*Department of Chemistry, University of Wisconsin-Milwaukee, Milwaukee, Wisconsin 53201, U.S.A.


The scope of the Fischer-indole cyclization of 2-benzoyl-4-oxo-1,2,3,4-tetrahydro-β-carboline (2) with various arylhydrazines is reviewed.

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23 data found. 1 - 23 listed