HETEROCYCLES
An International Journal for Reviews and Communications in Heterocyclic ChemistryWeb Edition ISSN: 1881-0942
Published online by The Japan Institute of Heterocyclic Chemistry
Regular Issue
Vol. 24, No. 6, 1986
Published online:
■ The Structures of Four New Diterpenoid Alkaloids
Antonio G. González, Gabriel de la Fuente,* Matías Reina, and Rafael Díaz Acosta
*Instituto de QUímica Orgánica, Instituto de Productos Naturales Orgánicos, C. S. I. C./ Unversidad de La Laguna, La Laguna, Tenerife, Canary Islands, Spain
Abstract
Together with karakoline, dihydrogadesine and 14-acetyldihydrogadesine, the new alkaloids 14-benzoylgadesine and 14-benzoyldihydrogadesine were isolated from Delphinium cardiopetalum. The new bases gadeline and 14-acetylgadesine were also isolated from Delphinium pentagynum. The structures of the new compounds were determined with the aid of 1H and 13C-nmr spectroscopy and chemical correlation to known alkaloids. The 13C-nmr chemical shifts for gadesine, dihydrogadesine and 14-acetyldihydrogadesine are also presented.
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■ Synthesis of Vinca Alkaloids and Related Compounds XXX. Total Synthesis of (±)-Tacamine, (±)-Apotacamine, and Their 20-Epimers
Lajos Szabó, Ede Márványos, Gábor Tóth, Csaba Szántay Jr., György Kalaus, and Csaba Szántay*
*Central Research Institute for Chemistry, Hungarian Academy of Sciences, H-1025 Budapest, Pusztaszeri ut 59-67, P.O.Box 17, Hungary
Abstract
Starting from iminium salt 3 two different methods have been elaborated for the synthesis of (±)-tacamine 1, (+)-apotacamine 2 and their 20-epimers .
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■ Studies in Cycloaddition Reactions: Regiospecific Cycloaddition Reactin of Nitrile Imines with 2H-1-Benzopyran-2-thione
Arpan Kumar Baruah, Dipak Prajapati, and Jagir Singh Sandhu*
*Division of Drug and Pharmaceutical Chemistry, Regional Research Laboratory, Jorhat 785 006, Assam, India
Abstract
Nitrile imines (1) reacted with 2H-1-benzopyran-2-thione to afford cycloadducts (3) in good yields. There was no evidence for the formation of any other regioisomer or the reaction occurring at the thione site.
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■ Novel Reductive Opening of 5,6-Dihydro-2H-pyran RIng
Janusz Jurczak,* Tomasz Bauer, and Kjell Ankner
*Institute of Organic Chemistry, Polish Academy of Sciences, ul. Kasprzaka 44/52, P.O.Box 58, PL-01-224 Warszawa 42, Poland
Abstract
Oxidation of 2-methoxy-5,6-dihydro-2H-pyran derivatives (4 and 5), followed by reduction of the resulting peroxides with sodium borohydride afforded enantiomerically pure open-chained compounds 9, 10, 11, and 12, which can serve as chiral building blocks.
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■ Regioselectivity of 1,3-Dipolar Cycloadditions Controlled by Remote Substitution and Lewis Acid Catalysts
Joaquín Plumet,* Gerardo Escobar, Cristina Manzano, Odón Arjona, Pierre-Alain Carrupt, and Pierre Vogel
*Departamento de Química Orgánica I., Facultad de Química, Universidad Complutense de Madrid, Ciudad Universitaria, E-28040 Madrid, Spain
Abstract
In the presence of ZnI2, benzonitrile oxide adds to the C=C double bond of 2-endo-acetoxy-7-oxabicyclo[2.2.1]hept-5-ene-2-exo-carbonitrile with interesting regioselectivity.
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■ Synthesis of 6,9-Epithiotachysterol3 and Related Compounds
Jacek W. Morzycki*
*Department of Chemistry, University of Warsaw, Pasteura St.1, 02-093 Warsaw, Poland
Abstract
The synthesis of 6,9-epithiotachysteryl3 acetate 7 and some other B-thiophene-des-A-steroids is described.
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■ Trifluoropyruvic Acid Hydrate in Heterocyclic Cynthesis Part III: A Novel Synthesis of 4-(Trifluoromethyl)-oxazolones and Other Related Compounds
Mohamed El-said Mustafa, Akio Takaoka, and Nobuo Ishikawa*
*Department of Chemical Technology, Faculty of Engineering, Tokyo Institute of Technology, 2-12-1,Oh-Okayama, Meguro-ku, Tokyo 152-8552, Japan
Abstract
Acid-catalyzed reaction of trifluoropyruvic acid hydrate (1) with nitriles is reported. The structure of the resulting compounds is also investigated.
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■ A Synthesis of 4-Cyano-hexahydro-1,5-imino-3-benzazocine-7,10-dione; a Potential Intermediate to Saframycin Synthesis
Hideshi Kurihara, Hiroshi Mishima, and Mamoru Arai*
*Sankyo Research Laboratories, Sankyo Co., Ltd., 1-2-58 Hiromachi, Shinagawa-ku, Tokyo 140-8710, Japan
Abstract
A simple and efficient synthesis of 4-cyano-1,2,3,4,5,6-hexahydro-1,5-imino-9-methoxy-8-methyl-3-benzazocine-7,10-dione (2a) is described starting from the corresponding lactam (3). Reduction of the lactam (3) with DIBAH followed by oxidation with HNO3 and neutralization of the resulting quinone in the presence of KCN afforded an α-aminonitrile derivative as the single product; the stereochemistry of the introduced cyano group being determined to be α-axial.
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■ A Facile Synthesis of 4-Aryl-2H-1,4-benzothiazin-3(4H)-ones: Reaction of N,N-Diarylacetamides with Thionyl Chloride
Hisatoshi Konishi,* Masayuki Takishita, Hiroaki Koketsu, Tamon Okano, and Jitsuo Kiji
*Department of Materials Science, Faculty of Engineering, Tottori University, 4-101 Koyama-minami, Tottori 680-8552, Japan
Abstract
The reaction of N,N-diarylacetamides with thionyl chloride yielded 4-aryl-2,2-dichloro-2H-1,4-benzothiazin-3(4H)-ones, which reacted with methanol to give 2,2-dimethoxy derivatives in good yield
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■ Synthesis of N-Carboxydehydrotyrosine Anhydride and Its Transformation to Useful Dehydrotyrosine Derivatives
Chung-gi Shin,* Yasuchika Yonezawa, and Takumi Obara
*Departmnet of Applied Chemistry, Faculty of Engineering, Kanagawa University, 3-27-1 Rokkakubashi, Kanagawa-ku, Yokohama 221-8686, Japan
Abstract
N-Carboxydehydrotyrosine anhydride (ΔTyr·NCA) was first synthesized from p-methoxymethoxybenzaldehyde and 2-azidoacetate via N-benzyloxycarbonyl-O-methoxymethoxydehydrotyrosin by five steps. The facile stepwise protections of δTyr·NCA gave many useful dehydrotyrosine derivatives.
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■ A Novel Ring Contraction of Lumazines to Theophyllines
Takashi Sugimoto,* Noriko Nishioka, Shizuka Murata, and Sadao Matsuura
*Human Informatics, Graduate of School, Nagoya University, Chikusa, Nagoya, Aichi 464-8601, Japan
Abstract
An unusual ring contraction of 7-methoxy-1,3-dimethyllumazines proceeded by an activated aluminum in methanolic ammonia to give 8-alkyltheophyllines.
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■ Pagisulfine — The First Sulfur-containing Indole-monoterpene Alkaloid
Maryse Bert, Geneviève Baudouin, François Tillequin, and Michel Koch*
*U.A. au C.N.R.S.n°484, Faculté des Sciences Pharmaceutiques et Biologiques, Université René Descartes, 4, Avenue de l‘Observatoire, F-75006 Paris, France
Abstract
The first sulfur-containing indole-monoterpene alkaloid, pagisulfine (1) has been isolated from the stem bark of Pagiantha cerifera (Pancher et Sébert) Markgraf. Its structure has been determined by spectroscopic studies. Its absolute stereochemistry has been estaiblished by its synthesis, using vobasine as starting material.
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■ Effect of a Silyl Group on the Regio- and Stereoselectivity in 1,3-Dipolar Cycloaddition
Yoshiyasu Terao, Masahiro Aono, and Kazuo Achiwa*
*Schol of Pharmaceutical Sciences, University of Shizuoka, 52-1 Yada, Shizuoka 422-8526, Japan
Abstract
Certain effect of a silyl group on the regio- and stereoselectivity in 1,3-dipolar cycloaddition has been demonstrated by cycloaddition of the thiocarbonyl ylide with a silyl group at the termini to unsymmetrical dipolarophiles.
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■ An Improved Synthetic Method for 5-Aryl-2-furancarbaldehyde
Maurizio D’Auria,* Roberto Antonioletti, Antonella De Mico, and Giovanni Piancatelli
*Dipart.Stud.Chem.Mol.Biol, Facolta di Farmacia, Università a degli Studi di Roma "La Sapienza", Piazza Aldo Moro, 5 - 00185 Roma, Italy
Abstract
An improved synthetic method for the preparation of 5-aryl-2-furancarbaldehyde via a photochemical arylation of 5-iodo-2-furancarbaldehyde is described.
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■ Highly Stereoselective Synthesis of cis- and trans-4-Benzoyl-2-oxozentidines
Benito Alcaide, Gema Domínguez, Gerardo Escobar, Ursula Parreño, and Joaquín Plumet*
*Departamento de Química Orgánica I., Facultad de Química, Universidad Complutense de Madrid, Ciudad Universitaria, E-28040 Madrid, Spain
Abstract
The reaction of the system acid chloride-triethylamine with 1,2-iminoketones yields exclusively cis-β-lactams, which may be isomerized to the corresponding trans isomers in a straightforward manner.
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■ A Convenient Synthesis of 5-(4-Pyridinyl)-2(1H)-pyridones
Woei-Ping Fang, Puh Shieh, and Min-Jen Shiao*
*Institutue of Chemistry, Academia Sinica, 128, Yan-Chiu-Yuan Road, Sec II, Nankang, Taipei,11529, Taiwan, R.O.C.
Abstract
A convenient synthesis of 3,4-bipyridine derivatives is reported. The addition of lithium salt derived from 2-alkoxy-5 bromopyridines 3a and 3b to N-ethoxycarbonylpyridinium chloride 4a gave the corresponding unstable 1,4-dihydropyridines which were readily oxidized by air to the 3,4’-bipyridines 6a and 6b. Compounds 6a and 6b can he converted into 5-(4-pyridinyl)-2(1H)-pyridones by hydrogenolysis and by alkylation in basic conditions.
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■ Synthesis and Conformational Analysis of 9,10,11,12,12a,13-Hexahydro-7H-naphtho[1,2-b]quinolizidine
María Fernández, Gregorio G. Trigo, and Mónica M. Söllhuber*
*Departamento de Química Orgánica y Farmacéutica, Facultad de Farmacia, Universidad Complutense de Madrid, Ciudad Universitaria, 28040 Madrid, Spain
Abstract
The synthesis of 9,10,11,12,12a,13 -hexahydro-7H-naphtho[1,2-b]quinolizine, which has structural similarity to antitumor alkaloid cryptopleurine (1), has been accomplished by a sequence involving as a key step the Friedel-Crafts acylation of 1-(2-naphthylmethyl)pipecolinic acid (9). Ir,1H, and 13C nmr data indicate a trans-fused quinolizidine conformer for naphtho[1,2-b]quinolizidine (14).
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■ New Acridone Alkaloids from Citrus junos Tanaka
Motoharu Ju-ichi,* Mami Inoue, Kuniko Aoki, and Hiroshi Furukawa
*Faculty of Pharmaceutical Science, Mukogawa-Women’s University, 11-68 Koushien Kyuban-Cho, Nishinomiya, Hyogo 663-8179, Japan
Abstract
Two new acridone alkaloids, junosine (1) and 5-methoxynoracronycine (2), were isolated from the bark of Citrus junos (Rutaceae) and their structures were elucidated on the basis of the spectral and chemical studies.
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■ Synthesis and Structure of 6-Phenylcyclophosphamides
Yun-Er Shih,* Jy-shih Wang, and Ling-Kang Liu
*Institutue of Chemistry, Academia Sinica, 128, Yan-Chiu-Yuan Road, Sec II, Nankang, Taipei,11529, Taiwan, R.O.C.
Abstract
6-Phenylcyclophosphamides have been synthesized from methyl benzoate and acetonitrile to benzoyl acetonitrile followed by reduction to amino alcohol and condensation with bis(2-chloroethyl)phosphoramidic dichloride. The two diastereomers have been separated and their structures have been assigned on the basis of ir, P-31 nmr and X-ray crystallography.
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■ Hetisine 13-O-Acetate, a New Diterpenoid Alkaloid from Delphinium nuttallianum Pritz
Michael Benn,* John F. Richardson, and Walter Majek
*Department of Chemistry, The University of Alberta, Calgary, Alberta, T2N, 1N4, Canada
Abstract
Hetisine-13-O-acetate was isolated from D. nuttallianum and its structure was deduced by MS, 1H and 13C nmr and proven by X-ray crystallography of the perchlorate salt.
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■ Synthesis of β-Lactams from α,β-Unsaturated Sugar δ-Lactones
Irma Panfil, Marek Chmielewski,* and Czeslaw Belzecki
*Institute of Organic Chemistry, Polish Academy of Sciences, ul. Kasprzaka 44/52, P.O.Box 58, PL-01-224 Warszawa 42, Poland
Abstract
Adduct 8 easily available by 1,3-dipolar cycloaddition of nitrone 1 and lactone 6 was transformed into β-lactams having a carbohydrate side chain at the position C-3 of the azetidinone ring. Basic chemical transformations of the 4-oxotetrahydropyrano[3,4-d]isoxazolidine skeleton have been described.
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■ Transformation of 6-Methylthiopyrazolo[3,4-d]pyrimidine Derivative by Action of Hydrazine and Synthesis of Novel Pyrazolotrizolopyrimidines
Jan Svetlík*
*Drug Research Institute, Palárikova 31, 811 04 Bratislava, Slovakia
Abstract
Nucleophilic displacement of the methylthio group during hydrazinolysis of 2,5-dihydro-2,5-dimethyl-6-methylthio-4H-pyrazolo[3,4-d]pyrimidin-4-one led unexpectedly to a 5-amino-6-hydrazino substituted product. A possible course for this reaction has been proposed. On treatment with ortho esters a novel tricyclic heterocycle, pyrazolo[4,3-e]-1,2,4-triazolo[4,3-a]pyrimidine, was formed.
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■ Preparation of Cyclic Carbonates and 2-Oxazolidones Using Di-2-pyridyl Carbonate
Sunggak Kim* and Young Kwan Ko
*Department of Applied Chemistry, Korea Advanced Institute of Science and Technology, P.O.Box 150 Chong-Yang-ni, Seoul 131, Korea
Abstract
Cyclic carbonates and 2-oxazolidones are conveniently prepared in high yields by the reaction of diols and β-amino alcohols with di-2-pyridyl carbonate. It is of synthetic significance that the formation of cyclic carboantes in refluxing toluene occurs under essentially neutral conditions.
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■ Synthesis of Pyrano, Thiopyrano, and Pyrido[3,2-d]pyrazoles
Saoud A. Metwally,* Mansour I. Younes, and Amal M. Nour
*Chemistry Department, Faculty of Science, Assiut University, Assiut 71516, Egypt
Abstract
The title compounds pyrano[3,2-d]pyrazoles (3) were obtained by the action of polyphosphoric acid on the 3-methyl-4-(1-aryl-3-aryl-3-oxopropyl)-2-pyrazolin-5-one, after neutralisation with sodium bicarbonate. Interaction of phosphorous pentasulphide with the starting compounds (2) in dry xylene gives rise to thiopyrano[3,2-d]pyrazoles (4) but pyrido[3,2-d]pyrazoles (5) were obtained by the action of ammonium acetate on the compound (2) in the presence of glacial acetic acid.
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■ Total Synthesis of Caerulomycin
Bipin D. Alreja, Samba L. Kattige, Bansi Lal, and Noel J. de Souza*
*Department of Chemistry, Research Centre, Hoechst India Limited, Mulund, Bombay 400 080, India
Abstract
Caerulomycin, a metabolite of Streptomyces caeruleus, is (E)-4-methoxy-2,2’-bipyridyl-6-aldoxime. Its synthesis and that of its (Z)-isomer is described starting from methyl picolinate and 3,5-dimethylisoxazole.
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■ Hypervalent Iodine Oxidation of Flavonols Using [Hydroxy(tosyloxy)iodo]benzebe in Methanol
Robert M. Moriarty,* Om Prakash, Hikmat A. Musallam, and Vijendra K. Mahesh
*Department of Chemistry, University of Illinois at Chicago, 845 West Taylor St., Chicago, IL 60607-7061, U.S.A.
Abstract
Hypervalent iodine oxidation of various flavonols (1a-1f) and α-naphthoflavonol (3) using [hydroxy(tosyloxy)iodo]benzene (HTIB) in methanol leads to the formation of 2,3-dimethoxy-3-hydroxyflavanones (2a-2f) and 2,3-dimethoxy-3-hydroxy-α-naphthoflavanone (4) respectively. HTIB resembles periodic acid in its oxidative behavior towards flavonols.
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■ The Synthesis of 2-Phenyl-3-nitro-3,4-dihydro-2H-1-benzopyrans
Rajender S. Varma, Miryam Kadkhodayan, and George W. Kabalka*
*Chemistry Department, University of Tennessee, Knoxville, Tennessee, 37196, U.S.A.
Abstract
A series of 3-nitrochromans, including a 3-phenyl-2-nitrodihydronaphtho[2,1-b]pyran, were synthesized in good yields by selective reduction of the corresponding 3-nitrochromenes using sodium brohydride in methanolic tetrahydrofuran.
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■ C(3)-Alkoxycephems
Douglas O. Spry* and Anita R. Bhala
*Lilly Reserach Laboratories, Lilly Corporate Center, Eli Lilly & Company, Indianapolis, IN 46285-4813, U.S.A.
Abstract
The C(3)-hydroxycephems 1 undergo the Mitsunobu reaction to give a series of heretofore unavailable C(3)-alkoxycephems 2.
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■ A New Formal Total Synthesis of (±)-Vincamine
Mauri Lounasmaa* and Reija Jokela
*Laboratory of Organic Chemistry, Helsinki University of Technology, P.O. Box 6100,FIN-02015 HUT, Espoo, Finland
Abstract
A new “one-pot” method was developed to transform the easily accessible enamine 2 to the crucial vincamine intermediate 4.
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■ A Facile One Step Synthesis of 4-Aminoindoles from 5-Halo-4-oxo-4,5,6,7-tetrahydroindoles
Masakatsu Matsumoto,* Yasuko Uchida, and Naoto Hatanaka
*Sagami Central Research Center, 4-4-1 Nishi-Ohnuma, Sagamihara, Kanagawa 229-0012, Japan
Abstract
Reaction of 5-halo-4-oxo-4,5,6,7-tetrahydroiondoles with amines initiates the amination of the carbonyl function and ensuing dehydrohalogenation leads to a successful formation of 4-aminoindoles.