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
Koji Nakanishi's Special Issues, Vol. 47, No. 1, 1998
Published online:
■ Isolation and Structure of Dolastatin 17
George R. Pettit,* Jun-Ping Xu, Fiona Hogan, and Ronald L. Cerny
*Cancer Research Institute, Department of Chemistry and Biochemistry, Arizona State University, Main Campus, P.O. Box 872404, Tempe, AZ 85287-2404, U.S.A.
Abstract
The unusual cyclodepsipeptide dolastatin 17 (1) was isolated from the Papua New Guinea sea hare Dolabella auricularia and found to contain a new acetylenic β-amino acid designated dolayne (Doy). Dolastatin 17 exhibited significant human cancer cell growth inhibitory activity (GI50 0.45-0.74 μg/mL range).
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■ In vitro Oxidation of Indoleacetic Acid by Crude Enzyme from Rice Husk—An Aspect of Preharvest Sprouting
Tadahiro Kato,* Norihiro Tomita, Masahiro Hoshikawa, Kazuhiro Ehara, Jyunko Shima, Norindo Takahashi, and Hiroshi Sugiyama
*Department of Chemistry, Faculty of Science, Science University of Tokyo, Kagurazaka 1-3, Shinjuku-ku, Tokyo 162-8601, Japan
Abstract
Indoleacetic acid was oxidized under oxygen atmosphere by the crude enzyme solution prepared by blending rice husk in buffer solution of pH 7.3. The major oxidation products (3, 4, and 5), characterized by physical and chemical methods, showed little effects on germination and growth of lettuce seeds while IAA inhibited completely the germination at 5 ppm. This evidence suggests that the amounts of IAA in embryos decreases due to the oxidation by water soluble oxidation enzyme existing in rice husk. The decrease of IAA may be related, in some aspect, to dormancy breaking and also preharvest sprouting of rice seeds. The synthesis and optical resolution of 2 was also achieved.
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■ Total Synthesis of (±)-Narlumicine, a Secophthalideisoquinoline Alkaloid
Maria Chrzanowska and Maria D. Rozwadowska*
*Facluty of Chemistry, Adam Mickiewicz University, ul. Grunwaldzka 6, 60-780 Poznán, Poland
Abstract
The first total synthesis of (±)-narlumicine (1), a secophthalideisoquinoline alkaloid, has been performed by addition of 6,7-methylenedioxyphthalide (4) lithium salt to 2-(N,N-dimethylaminoethyl)piperonal (3).
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■ Polyhetero[3,3]-sigmatropic Rearrangement of O(S)-Methyl-S(O)allyl-N-(9-acridinyl)-iminothiocarbonates
Pavol Kristian,* Slávka Hocová, Juraj Bernát, Tatiana Busová, and Igor Chomca
*Department of Organic Chemistry, P. J. Safárik University, Moyzesova 11, SK-04167 Kosice, Slovakia
Abstract
A new synthetic route to N-allyl-N-(9-acridinyl)thiocarbamic acid O-methyl esters (5a-c) and S-methyl esters (6a, b) via S→N (O→N) allylic transposition of O(S)-methyl-S(O)-allyl-N-(9-acridinyl)iminothiocarbonates (3a-c, 4a, b) was elaborated. The reaction represents a new convenient method for the synthesis of this type of acridine compounds.
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■ Simple One Step Syntheses of Indole-3-acetonitriles from Indole-3-carboxaldehydes
Fumio Yamada, Tomoko Hashizume, and Masanori Somei*
*Faculty of Pharmaceutical Sciences, Kanazawa University, 13-1 Takara-machi, Kanazawa 920-0934, Japan
Abstract
One step conversion method of indole-3-carboxaldehydes into indole-3-acetonitriles is developed. Applying the method, 4-nitro- (7a), 4-phenyl- (7b), 4-iodo- (7c), 4-methoxy- (7d), and 4-benzyloxyindole-3-acetonitrile (7e) are available in two steps from indole-3-carboxaldehyde (4).
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■ An Efficient Synthesis of 3-Phosphorylated 4(1H)-Pyridones and 4-Chloropyridines fromβ-Enaminophosphonates
Francisco Palacios,* Ana Ma Ochoa de Retana, and Julen Oyarzabal
*Departamento de Química Orgánica, Facultad de Farmacia, Universidad del País Vasco, Apartado 450, 01080 Vitoria-Gasteiz, Spain
Abstract
An easy and efficient synthesis of 4(1H)-pyridones (1) substituted with a phosphate group in the 3-position is described. The key step is an addition of β-enaminophosphonates (2) to acylketene (3) generated either horn diketene (4) or from the “diketene-acetone adduct”, 2,2,6-trimethyl-4H-1,3-dioxin-4-one (5). Subsequent treatment of 4(1H)-pyridones with phosphorus oxychloride in the presence of dimethylformamide afforded the substituted 4-chloropyridine (6).
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■ Racemic and Chiral Syntheses of Some Indolo[2,3-a]quinolizidine Alkaloids through a "Lactim Ether Route"
Tozo Fujii* and Masashi Ohba
*Faculty of Pharmaceutical Scicences, Kanazawa University, 13-1 Takara-machi, Kanazawa 920-0934, Japan
Abstract
The racemic and/or chiral syntheses of some Corynanthe-type indoloquinolizidine alkaloids and related bases, accomplished through a “lactim ether route” by the present authors’ group, are reviewed with 107 reference citations. As a result of these syntheses, the structures and/or absolute configurations of the Neisosperma alkaloid ochromianine [(-)-35], the Ophiorrhiza alkaloid ophiorrhizine [(-)-46], and the Neisosperma and Ochrosia alkaloid ochropposinine [(-)-49] have been unequivocally established.
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■ Intramolecular Reactions of Nitrilimines as a Fruitful Source of Heterocycles
Gianluigi Broggini, Giorgio Molteni, and Gaetano Zecchi*
*Dipartimento di Chimica Organica e Industriale, Universita di Milano, via Golgi 19, I-20133 Milano, Italy
Abstract
The multiform intramolecular reactivity of nitrilimines is presented in a systematic way, giving emphasis to its versatile potential in heterocyclic synthesis.
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■ Infrared Carbonyl Frequencies of Heterocyclic Lactones
J. Hodge Markgraf
*Department of Chemistry, Williams College, 47 Lab Campus Drive, Williamstown MA 01267-2692, U.S.A.
Abstract
Infrared carbonyl frequencies of heterocyclic lactones are tabulated on the basis of ring size, number and position of heteroatoms, substituents, unsaturation, and solvent effects.
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■ Biotinyl Diazirine Photophore: An Approach to High-resolution Photoaffinity Labeling for Probing Receptor-Ligand Interface
Yasumaru Hatanaka* and Yuichi Kanaoka
*Research Institute for Wakan-Yaku, Toyama Medical and Pharmaceutical University, 2630 Sugitani, Toyama, Toyama 930-0194, Japan
Abstract
The technique of photoaffinity labeling has become increasingly appreciated as a powerful chemical methodology for the detailed structural analysis of ligand binding domains. This review describes our recent approach to the development of new phenyldiazirine family, the design of biotinyl photoprobes, and their application in the field of glycobiology.