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. 31, No. 3, 1990
Published online:
■ The Synthesis and Structure of Chiral Di-N-p-toluenesulphonyl Diazacoronands Derived from L-Tartaric Acid
Janusz Jurczak,* Ryszard Ostaszewski, Giovanni D. Andreetti,* and Gianluca Calestani
*Institute of Organic Chemistry, Polish Academy of Sciences, ul. Kasprzaka 44/52, P.O.Box 58, PL-01-224 Warszawa 42, Poland
Abstract
Two chiral di-N-p-toluenesulphonyl diazacoronands 5 and 6, derived from L-tartaric acid (1), were synthesized by the modified Richman-Atkins prodecure. The structure of compound 5 was determined by X-ray analysis.
Published online:
■ Synthesis of Key Carbazoles — Intermediates for Polymethoxyellipticines and Olivacins
Robin J. Hall, Anthony H. Jackson,* Ana M. F. Oliveira-Campos, Maria-Joao R. P. Queiroz, and Patrick V. R. Shannon*
*School of Chemistry and Applied Chemistry, College of Cardiff, University of Wales, Cardiff CF1 3TB, Wales, U.K.
Abstract
The synthesis of three polymethoxycarbazoles, key intermediates for the synthesis of new 6H-pyrido[4,3-b]carbzoles, is described. The required 3-formyl function, or its precursor, is introduced through three different strategies. The validity of these carbazoles for the synthesis of ellipticines and olivacines is demonstrated by the efficient synthesis of the new 7,8,9-trimetoxyellipticine.
Published online:
■ A Formal Total Synthesis of (6S,7S,9R,10R)-6,9-Epoxynonadec-18-ene-7,10-diol from D-Glucose
Mukund K. Gurjar* and Prathama S. Mainkar
*Indian Institute of Chemical Technology, Hyderabad 500 007, India
Abstract
An enantiospecific synthesis of (2R,4S,5S)-tetrahydro-4-hydroxy-5-pentyl-2-furfuraldehyde (benzoate) (2) and (benzylate) (3), key intermediates in the synthesis of the title marine natural product (1) from D-glucose is described.
Published online:
■ An Enantiocontrolled Rotue to Unnatural (+)-Physostigmine
Seiichi Takano,* Tsutomu Sato, Kohei Inomata, and Kunio Ogasawara
*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan
Abstract
ent-Esermetole (3), enantiomer of the key intermediate of physostigmine (1) and its other congeners, has been synthesized starting from the known optically active dihydronaphthalene (6) obtained via lipase mediated asymmetric hydrolysis.
Published online:
■ Cationic Polar Cycloaddition with Anodically Prepared α-Tri- and α-Difluoromethylated N,O-Acetals: Preparation of Fluoromethylated Tetra- and Dihydroquinoline Derivatives
Toshio Fuchigami,* Shinji Ichikawa, Zaghloul E. Kandeel, Akinori Konno, and Tsutomu Nonaka
*Department of Electronic Chemistry, Graduate School at Nagatsuta, Tokyo Institute of Technology, Nagatsuta, Midori-ku, Yokohama 226-8501, Japan
Abstract
Anodically prepared α-tri- and α-difluoromethylated N,O-acetals readily underwent [4++2] type polar cycloadditions with styrenes and phenylacetylene in the presence of a Lewis acid to provide the corresponding fluoromethylated tetra- and dihydroquinoline derivatives.
Published online:
■ Base-induced Condensation of Phenols Joined by Amides to Ketones: A Synthesis of Hydroxylated Isoquinolinones and Derivatives
Richard Friary,* John H. Schwerdt, Vera Seidl, and John G. Topliss
*Schering-Plough Research, Schering-Plough Corporation, 86 Orange Street, Bloomfield, New Jersey 07003, U.S.A.
Abstract
Pottassium carbonate in methanol saponified the acetate ester groups of certain meta-acetoxylated α-benzamido ketones and cyclized the resulting phenols in situ to give a series of hydroxylated isoquinolinones and derivatives.
Published online:
■ A Method for Easy Preparation of Optically Pure (S)-5-Hydroxy-2-penten-4-olide and (S)-5-Hydroxypentan-4-olide
Koshi Koseki,* Takashi Ebata, Hiroshi Kawakami, Hajime Matsushita, Yoshitake Naoi, and Kazuo Itoh
*Life Science Research Laboratory, Japan Tobacco Inc., 6-2, Umegaoka, Midori-ku, Yokohama, Kanagawa 227-8512, Japan
Abstract
A new method for preparation of (S)-5-hydroxy-2-penten-4-olide 1 and (S)-5-hydroxypentan-4-olide 8 starting from levoglucosenone 2 is described.
Published online:
■ Based-induced Conversion of N-Alkoxypyridinium Salts Bearing a Formyl Group in Their Alkoxyl Chain
Henri Sliwa,* Clarisse Randria-Raharimanana, and Guy Cordonnier
*Laboratoire de Chimie Organique, Université des Sciences et Techníques de Lille Flandres-Artois, F-59655 Villeneuve d’ Ascq Cedex, France
Abstract
Reaction of pyridine N-oxide with α-disubstituted 2-bromoaldehydes led to the expected N-alkoxypyridinium salts which were converted to 2-(α-hydroxyacyl)pyridines on base treatment.
Published online:
■ Atom Transfer Cyclization of α-Halonitrile and α-Halocarbonyl Compounds
Miwako Mori,* Yukiko Kubo, and Yoshio Ban
*Faculty of Pharmaceutical Sciences, Hokkaido University, Sapporo 060, Japan
Abstract
α-Halonitriles and α-haloester reacted with internal olefin in the presence of KI to give cyclized products in good yields via radical intermediate. α-Iodonitrile 1b afforded 2b and 2b’ merely upon heating.
Published online:
■ One-Pot Preparation of γ-Butyrolactone Derivatives from Olefinic Alcohols via Intramolecular Radical Cyclization Reaction
Hideo Togo* and Masataka Yokoyama*
*Department of Chemistry, Faculty of Sciences, Chiba University, 1-33 Yayoi-cho, Inage-ku, Chiba 263-8522, Japan
Abstract
γ-Butyrolactone derivatives were obtained in moderate yields to good yields via the radical decarboxylation of the mixed esters which were generated from olefinic alcholos by successive treatment with oxalyl chloride and N-hydroxy-2-thiopyridone.
Published online:
■ Stereoselective Reduction of t-Butyldimethylsiloxy Group of Ethyl 2-Trichloromethyl-4-t-butyldimethylsiloxy-1,3-dioxan-4-acetates
Koichi Homma and Teruaki Mukaiyama*
*Department of Applied Chemistry, Faculty of Science, Science University of Tokyo, Kagurazaka, Shinjuku-ku, Tokyo 162, Japan
Abstract
t-Butyldimethylsiloxy group of ethyl 4-t-butyldimethylsiloxy-2-trichloromethyl-1,3-dioxan-4-acetates, easily prepared from 2-trichloromethyl-1,3-dioxan-4-ones, was stereoselectively reduced with triethylsilane by using titanium tetrachloride s a promoter to afford ethyl cis-2-trichloromethyl-1,3-dioxan-4-acetaes.
Published online:
■ Improving Regioselectivity under Phase Transfer Conditions: Effect of Chemical Parameters and Kinetic Study of Indole N-Alkylation
Mohamed Bourak and Roger Gallo*
*ESIPSOI, U.A. 126 C.N.R.S., Fac Sciences et Tech. St. Jerome, 13013 Marseille Cedex 13, France
Abstract
The results obtained by changing the nature of catalyst, solvent, HaOH concentration, nature or ratio of reagents and reaction procedure are discussed for the alkylation of indole by benzyl halide under PTC conditions. Besides N-benzylindole other isomers are formed with the intermediate 3-benzylindole being detected at early reaction stage. Formation of benzyl alcohol (and ether) and of tertiary amine occurs in parallel. The relative rate constant with the leaving group chloride compared to bromide is 1/57, but the overall yield and selectivity in 1-alkylation is increased. Rate constants and activation parameters are reported. Butyl and heptyl halides show similar behavior. The results are discussed in light of the general problem of change in nucleophilic ambident reactivity of heterocycles induced under phase transfer conditions.
Published online:
■ Formation and Reactivity of Highly Stabilized Carbanions and Enolates by Pd-Catalyzed Alkylation of Heterocyclic Compounds
Tsutomu Sakakibara,* Takashi Kume, Kumiko Shimohara, Hiroshi Fujishima, Shunpei Hara, and Toshifumi Shimoda
*Institute of Chemistry, College of Liberal Arts, Kagoshima University, 1-21-35 Korimoto, Kagoshima 890-0065, Japan
Abstract
Highly stabilized carbanion and enolate salts, heterocycle-substituted sodiomalononitrile and sodiocyanoacetates, were synthesized via Pd-catalyzed ring-alkylation of bromoheterocyclic compounds and shown to be useful intermediates for the synthesis of various alkyl-substituted heterocyclic compounds.
Published online:
■ Studies in Sprioheterocycles: Part XXVIII: Investigation of the Reaction of 3-Aroylmethyleneindolin-2-ones with Thiosemicarbazide and Synthesis of Spiro[3H-indole-3.4’(3’H)-pyrimidin]-2(1H)-ones
Krishna C. Joshi, Renuka Jain, and Kanti Sharma*
*Department of Chemistry, R. L. Saharia Govt. College, Kaladera, Jaipur 302 004, India
Abstract
Simple and N-substituted 3-aroylmethyleneindolin-2-ones (IV) have been obtained by the reaction of indole-2,3-diones with methyl ketones followed by dehydration. The reaction of IV with thiosemicarbazide has been investigated to study the effect of substitution on N atom. Our studies revealed that IV (R=H), on reaction with thiosemicarbzide, afforded exclusively the hydrazone (V) but under exactly limilar conditions, N-methyl-3-aroylmethyleneindolin-2-ones (IV; R=CH3) afforded spiro[3H-indole-3,4’(3’H)-pyrimidin]-2(1H)-ones (IV).
Published online:
■ 4,10-Dinitro-2,6,8,12-tetraoxa-4,10-diazatetracyclo[5.5.0.05,903,11]dodecane
Vayalakkavoor T. Ramakrishnan, Murugappa Vedachalam, and Joseph H. Boyer
*Department of Chemistry, University of New Orleans, New Orleans, LA 70148, U.S.A.
Abstract
Glyoxal condensed with 1,4-diformyl-2,3,5,6-tetrahydroxypiperazine in the presence of sulfuric and nitrifc acids to give the title compound.
Published online:
■ Alkyl N-Nitro- and N-Nitrosopiperidin-2-ylcarbamates
Govindarajulu Kumar and Joseph H. Boyer*
*Department of Chemistry, University of New Orleans, New Orleans, LA 70148, U.S.A.
Abstract
N-Nitro- and N-nitrosopipecolic acid 1 and 6 were converted to 1-nitro- and 1-nitroso-2-aminopiperidine. The amines were isolated as methyl carbamate derivatives 4 and 11.
Published online:
■ Preparation of a New Chiral 5,6-Dihydropyridinium Synthon
Anna Diez, Huang Pé-Quiang, David S. Grierson, Henri-Philippe Husson, and Mario Rubiralta
*Laboratory of Organic Chemistry, Faculty of Pharmacy, University of Barcelona, Av. de Joan XXIII, s/n, 08028 Barcelona, Spain
Abstract
A new chiral synthon, oxazolidinonepiperidine 7, is prepared from intermediate 5, derived from (S)-(-)-ethyl lactate, by chemoselective reduction of the piperideinone carbonyl group followed by oxazolidinone ring closure.
Published online:
■ Buxapapilinine — A Novel Alkaloid from the Leaves of Buxus papillosa
Atta-ur-Rahman,* Zahida Iqbal, M. Iqbal Choudhary, and Talat Fatime
*H. E. J. Postgraduate Institute of Chemistry, University of Karachi, Karachi-75270, Pakistan
Abstract
A novel alkaloid buxapapilinine (1) has been isolated from the leaves of Buxus papillosa. Its structure has been investigated by extensive nmr studies.
Published online:
■ The Formation of 3,10β-Epoxy-B-homotriterpenes from 8β-Hydroxycycloartanyl Derivatives
Hiroshi Sakamaki,* Masanobu Ando, Hiroshi Sekine, Taro Matsumoto, Tsukasa Iwadare, and Yoshiyuki Ichinohe
*College of Science and Technology, Nihon University, 7-24-1 Narashinodai, Funabashi-shi, Chiba 274-0063, Japan
Abstract
Treatment of 3β,8β-dihydroxycycloartan-7-one (1b) with p-toluenesulfonic acid gave 3β,10β-epoxy-9,10-secocycloart-8-en-7-one (2), 3β-hydroxy-9,10-secocycloarta-1(10),8(9)-dien-7-one (3) and an unidentified compound (4). In addition, transformations of tetrahdyropyranyl and ethoxyethyl derivatives (1c and 1d) into 2 with acid catalysts are described.
Published online:
■ A Facile One-Step Synthesis of Novel Polysubstituted Pyridines via the Tandem-Addition Rearrangement Hetaryne Reaction
Subhash P. Khanapure and Edward R. Biehl*
*Department of Chemistry, Southern Methodist University, P.O. Box 750314, Dallas, TX 75275-0314, U.S.A.
Abstract
Polysubstituted pyridines have been prepared in fair yields by a one-step reactionn of heteroarene 3-bromo-2,3-dimethoxy-5-(methoxymethyl)pyridine 3 and lithio alkyl- and lithio aryl-acetonitriles via the heteroaryne 13 generated from 3 by LDA in THF. Most lithio arylacetonitriles 4a-f yield rearranged products 5a-f by the tandem-addition rearrangement pathway and a 2:1 to 3:1 mixture of normal hetaryne products 6a-f and 7a-f. The other nitriles 4g-l give mixtures of the usual hetaryne products in ratios of 3:1 to 4:1, 6g-l:7g-l, respectively.
Published online:
■ New Amaryllidaceae Alkaloids from Narcissus papyraceus Ker-Gawler
Rafael Suau,* Rodrigo Rico, Ana I. García, and Ana I. Gómez
*Departamento de Quimica Orgánica, Facultad de Ciencias, Universidad de Málaga, Campus de Teations, E-29071 Málaga, Spain
Abstract
Three new alkalods, O-methylpapyramine (1), O-methylmaritidine (2) and 9-O-demethylhomolycorine N-oxide (3) have been isolated from aerial parts of Narcissus pypyraceus Ker-Gawler, together with lycorine, papyramine, pseudolycorine, homolycorine and 9-O-demthylhomolycorine.
Published online:
■ Synthesis of Milrinone, a Cardiotonic Agent
Min-Jen Shiao,* Li-Ming Shyu, and Chieh-Fu Chen
*Institutue of Chemistry, Academia Sinica, 128, Yan-Chiu-Yuan Road, Sec II, Nankang, Taipei,11529, Taiwan, R.O.C.
Abstract
A new synthesis of milrione (6) from 6-methyl-5-(4-pyridiyl)-2(1H)-pyridone (4) is reported. A convenient synthesis of 3,4’-bipyridines (3a) and (3b) is achieved. 3a and 3b can be converted into pyridone 4 by hydrogenolysis and hydrolysis, respectively. Bromination at C-3 of the pyridone ring of 4 followed by cyanation affords milrinone (6).
Published online:
■ Synthesis of (S)-3-Carbobenzoxyamino-1-amino-2-azetidinones
Hisao Iwagami* and Naohiko Yasuda
*Central Research Laboratories, Ajinomoto Co., Inc., 1-1, Suzuki-cho, Kawasaki-ku, Kawasaki, Kanagawa 210-0801, Japan
Abstract
Cyclization of amio acid hydrazide afforded a new class of heteroatom activated β-lactam. These compounds are potent parent nuclei which possess significant biological activity.
Published online:
■ Synthesis of 2-Azolylcycloalkanols
Akira Murabayashi* and Yasuo Makisumi
*Aburahi Laboratories, Shionogi Research Laboratories, Koka-cho, Shiga 520-34, Japan
Abstract
New 2-azolylcycloalkanol derivatives (13-38) were synthesized stereoselectively by Grignard reaction of 2-azolylcyclohexanones (7, 8), and particularly 2-azolylcycloheptanones (9, 10) afforded one of the diastereomers of 2-azolylcycloalkanols stereospecifically because the reagent attacked the carbonyl group from the less hindered side of the magnesium complex intermediate. These azolylcycloalkanols (13-38) were tested for antifungal activities.
Published online:
■ Revised Structures of Linderatone and Methyllinderatone
Kazuhiko Ichino, Hitoshi Tanaka, and Kazuo Ito*
*Faculty of Pharmacy, Meijo University, 150 Yagotoyama, Tenpaku, Nagoya 468-8503, Japan
Abstract
The structure of a terpenylflavonone, linderatone, was revised to 6-terpenylflavonone by 1H-13C long-range cosy experiment. Therefore, the structure of methyllinderatone was also revised to 4.
Published online:
■ Synthesis of 7-Amino-1,2,3,4-tetrahydroacridine-9-carboxylic Acid and Its Derivatives. Reductionof Nitro Compounds under Alkaline Conditions
Mohammed T. Shipchandler* and Philip G. Mattingly
*Diagnostics Division, D-93C and D-90U, AP-20, Abbott Laboratories, Abbott Park, IL 60064, U.S.A.
Abstract
Condensation of 5-nitroisatin (1) with cyclohexanone in the presence of alcoholic potassium hydroxide, unexpectedly, produced 7-amino-1,2,3,4-tetrahydroacridine-9-carboxylic acid (2) instead of 7-nitro derivative. The general nature of this reaction was shown by substituting several cyclic ketones in this reaction. A radical anion intermediate is proposed to explain this unusual noncatalytic reduction.
Published online:
■ Synthesis and Properties of 6H-Benzo[hi]pyrrolo[2,1,5-cd]indolizin-6-ones
Michihiko Noguchi,* Takashi Yamamoto, and Shoji Kajigaeshi
*Department of Industrial Chemistry, Faculty of Engineering, Yamaguchi University, Tokiwadai, Ube 755, Japan
Abstract
The electronic features and chemical behaviors of 3-phenyl-6H-benzo[hi]prrolo[2,1,5-cd]indolizin-6-one (1) were discussed comparing with those of 4-one regio-isomer, 3-phenyl-4H-benzo[hi]pyrrolo[2,1,5-cd]indolizin-4-one (2).
Published online:
■ The Synthesis of 2’-Deoxy-5-trifluoromethyluridine Utilizing a Coupling Reaction
Hiroshi Kawakami,* Takashi Ebata, Koshi Koseki, Hajime Matsushita, Yoshitake Naoi, Kazuo Itoh, and Nobuhiro Mizutani
*Life Science Research Laboratory, Japan Tobacco Inc., 6-2, Umegaoka, Midori-ku, Yokohama, Kanagawa 227-8512, Japan
Abstract
The coupling reaction between 1-α-chloro-2-deoxyribose derivatives and silylated 5-trifluoromethyluracil was examined. The best stereoselectively was obtained when the reaction was carried out using a large amount of silylated base in the presence of anhydrous zinc chloride.