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. 27, No. 7, 1988
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■ A New Prostaglandin Intermediate from Aucubigenin
Enrico Davini, Carlo Iavarona, and Corrado Trogolo
*Centro CNR per lo Studio della Chimica delle Sostanze Organiche Naturali, Dipartmento di Chimica, Università degli Studi di Roma "La Sapienza", Piazzale Aldo Moro 5, 00185 Roma, Italy
Abstract
The synthesis of the new prostanoid intermediate 2 (Corey lactone analogue) from iridoid aglycone aucubigenin 2 is described.
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■ Acid Catalyzed Dimerization of the Pyranocoumarin Xanthoxyletin: Formation of a "Diels-Alder" Dimer Analogous to the Paraensidimerines
Sharon E. Parker, Alexander I. Gray, and Peter G. Waterman*
*Phytochemistry Research Labratories, Department of Pharmacy (Pharm. Chem.), University of Strathclyde, Glasgow G1 1XW, Scotland, U.K.
Abstract
Acid-catalyzed dimerization of xanthoxyletin has given, in low yield, a dimeric compound which has been identified as a Diels-Alder addition product in which the C-4’ and C-3’ positions of one monomer have linked, respectively, with one of the C-2’ methyls and C-4’ of the other. While a similar dimerization reaction is known in a number of pyranoquinolone alkaloids from the Rutaceae this is the first report of its occurrence among pyranocoumarins.
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■ Structure and Stereochemistry of Corytensine, a New Phthalideisoquinoline Alkaloid from Corydalis Ochotensis
Tian-Shung Wu,* Shiow-Chyn Huang, Sheng-Teh Lu, Yang-Chang Wu, Donald R. McPhail, Andrew T. McPhail, and Kuo-Hsiung Lee
*Department of Applied Chemiastry, Providence College of Arta and Science, Shalu 43309, Taichung Hsien, Taiwan, R.O.C.
Abstract
A new phthalideisoquinoline alkaloid, corytensine, has been isolated from Coryalis ochotensis Turcz., and, its structure and stereochemistry have been established as (1) from spectral data and a single crystal X-ray analysis.
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■ Effects of the Ring Size on the Regioselectivity of Amino-Claisen Rearrangement of Unsymmetrically Fused Anilinium Derivatives
Hajime Katayama* and Kimiyoshi Kaneko
*Niigata College of Pharmacy, 5-13-2 Kamishin‘ei-cho, Niigata 590-2081, Japan
Abstract
The site of meta rearrangement in quaternary amino-Claisen rearrangement is found to be controlled by the size of the fused rings. This regioselectivity is also predictable from the magnitudes of the chemical shifts differences between the two meta carbons.
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■ An Intramolecular Ring Contraction Approach to the Synthesis of Indolizidine Alkaloids
Emmanuel Zeller and David S. Grierson*
*Institut des Chimie des Substances Naturelles, C.N.R.S., 1 avenue de la Terrasse, Bat. 27, 91198 Gif-sur-Yvette Cedex, France
Abstract
Reaction of the anion of synthon 5 with PrBr followed by reductive decyanation gave the key intermediate 8. Ring opening of 8, a treatment with diethyl cyanophosphonate, produced 9. Compound 9 reacted with K ptus 18-crown-6 in THF to give a 9:1 mixture of indolizidines 10 and 11.
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■ Nitriles in Heterocyclic Synthesis: 1-Cyanoformanilide as Precursor for a Variety of Heterocyclic Ring Systems
Sherif Mourad Sherif, Raffat Milad Mohareb, Galal Eldin H. Elgemeie, and Rajendra Prasad Singh
*Department of Chemistry, Faculty of Science, University of Cairo, Giza, Egypt
Abstract
A variety of polyfunctionally substituted azoles and azines could be synthesized utilizing 1-cyanoformanilide (1) as a precursor.
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■ A Convenient Synthetic Method of 2-Substitute Indoles and Its Application for the Synthesis of Natural Alkaloid, Borrerine
Masanori Somei,* Shunsuke Sayama, Katsumi Naka, and Fumio Yamada
*Faculty of Pharmaceutical Sciences, Kanazawa University, 13-1 Takara-machi, Kanazawa 920-0934, Japan
Abstract
A simple synthetic method of 2-substituted indoles is developed. Total synthesis of natural alkaloid, borrerine, is also reported.
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■ Reaction of 3-Aclypyridinium Salts with Electrophilic Olefins. A One-pot Ring Annelation Reaction of Pyridines
Hans Bieräugel, Karel M. J. Brands, and Upendra K. Pandit*
*Laboratory of Organic Chemistry, Institute of Molecular Chemistry, University of Amsterdam, Nieuwe Achtergracht 129, 1018 WS Amsterdam, The Netherlands
Abstract
The base-mediated addition of N-alkylated 3-pyridyl ketones (2a-d) to diethyl methylenemalonate (3) and ethyl α-phenylthioacrylate results in the formation of hexahydroisoquinoline derivatives in a one-pot reaction.
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■ Exceptionally Facile Reduction of Carboxylic Acid Salts to Aldehydes by 9-Borabicyclo[3.3.1]nonane
Jin Soon Cha,* Se Yeon Oh, Kwang Woo Lee, Mal Sook Yoon, Jae Cheol Lee, and Jin Euog Kim
*Department of Chemistry, Yeungnam University, Kyongsan 712-749, Korea
Abstract
Both sodium and lithium salts of carboxylic acids in the presence of 2 equiv of 9-borabicyclo[3.3.linonane(9-BBN) are readily converted to the aldehydes in approximately 1-3 h at room temperature in high yields. Thus, simple aliphatic carboxylic acid salts, such as butyric, hexanoic, decanoic, stearic, isobutyric, isopentanoic, pivalic, cyclopropanecarboxylic, and cyclohexanecarboxylic acid salts, readily undergo the reaction to aldehydes in yields of 84-99%. Derivative, such as diphenylacetic acid salts, undergoes the reaction in a h s t quantitative yields. Even dicarboxylic acid salts, such as α-camphoric and 1,10-decanedicarboxyilc acid salts, work equally well. The yields of aromatic carboxylic acid salts are variable ranged from 54 to 83% except for the case of terephthalic acid salts being 99%.
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■ Facile Route to 2,3-Disubstituted Chemonones via Chromone-3-carboxaldehyde Activated by Silylation
Hideharu Iwasaki, Takashi Kume, Yosuke Yamamoto, and Kin-ya Akiba*
*Department of Chemistry, Faculty of Science, Hiroshima University, 1-3-1 Kagamiyama, Higashi-Hiroshima, Hiroshima 739-8526, Japan
Abstract
Aldol type condensation of chromone-3-carboxaldehyde (1) with active methylenes in the presenoe of t-butyldimethylsilyl triflate afforded silylated aldol adducts (4), which were further converted to 2,3-disubstituted chromanones by reaction with enol silyl ethers via the corresponding 4-siloxypyrylium salts.
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■ Synthesis of Corynantheine Alkaloids with (19E)-Ethylidene Group: On the Structures of Rhazimanine and Bhimberine
Takeaki Naito, Tetsuro Shinada, Okiko Miyata, Ichiya Ninomiya,* and Toshimasa Ishida
*Kobe Women’s College of Pharmacy, Motoyamakita, Higashinad, Kobe, Hyogo 658, Japan
Abstract
Syntheses of four indoloquinolizidine alkaloids having a (19E)-ethylidene group at the 20-position, (±)-isositsirikine (1), (±)-16-epiisositsirikine (2), and the proposed structures of (±)-rhazimanine (3) and (±)-bhimberine (4), were accomplished and have suggested that the structures of rhazimanine (3) and bhimberine (4) require revision.
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■ Synthesis of 7,12-Dihydropyridopyrroloindoles (Azapyridodiindoles) via the Fischer Indole Cyclization. A Search for Water Soluble Benzodiazepine Receptor Ligands.
Yun-chou Tan, Mark L. Trudell, and James M. Cook*
*Department of Chemistry, University of Wisconsin-Milwaukee, Milwaukee, Wisconsin 53201, U.S.A.
Abstract
The thermally-induced Fischer indole cyclization of the 3-acylindole 7 with various substituted hydrazinopyridines provides a simple route to the 7,12-dihydropyridopyrroloindoles 2, 4 and 5, respectively. In contrast, the corresponding acid-catalyzed process yielded only 4-amino-β-carboline 15. Moreover, attempts to prepare the 3-aza-analog 3, from reaction of 7 and 4-hydrazinopyridine 12 under thermal or acidic conditions, provided only 15. The difference between the reactivity of the 4-substituted pyridine 12, in comparison to 11 or 13, is discussed in terms of pKa values and intermediates in the Fischer indole cyclization.
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■ Studies on the Alkaloids from Aconitum Polyschistum Hand-Mazz. Part II.
Hongcheng Wang, Aina Lao, Yasuo Fujimoto,* Kimiko Kobayashi, Toshio Sakurai, and Takashi Tatsuno
*The Institute of Physical and Chemical Research, Wako-shi, Saitama 351-0198, Japan
Abstract
A new alkaloid, polyschistine D (1), a new natural product, benzoyldeoxyaconine (2), and three known alkaloids, benzoylaconine (3), deoxyaconitine (4), and aconitine (5) have been isolated from the roots of Aconitum polyschistum Hand-Mazz collected Sichuan province in China. The structures of polyschistine D (1) and benzoyldeoxyaconine (2) were confirmed on the basis of their spectral data and the chemical correlations.
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■ Optimization of the Synthesis of N(1)-(2-Aminoethyl)-NAD(P)
Andreas F. Bückmann*
*Research Group Microbial Ecology, GBF - National Research Center for Biotechnology, Mascheroder Weg 1, D-38124 Braunschweig, Germany
Abstract
The alkylation of NAD(P) to N(1)-(2-aminoethyl)-NAD(P) with ethyleneimine in aqueous solution was optimized. First the pH-dependency of the alkylation of the N (1)-position of the adenine nucleus of NAD was studied in the pH range 2-5.5 at 20°C. followed by adjusting the temperature and the concentration of ethyleneimine to achieve acceptable reaction times. The results were directly applicable with respect to the synthesis of N(1)-(2-aminoethyl)-NADP.
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■ Encounter of an Inferior Intramolecular Cyclization in an Approach toward the Synthesis of 10-Oxo-2-thia[3.2]metacyclophane: Preparation of Two Isomeric Dioxo-2,19-dithia[3.2.3.2]metacyclophanes
Yee-Hing Lai* and Lay-Hoon Yeo
*Department of Chemistry, National University of Singapore, 10 Kent Ridgh Crescent, 119260, Singapore
Abstract
The sodium sulfide coupling of 1,2-bis(3-bromomethhyl)phenylethanone, prepared in seven steps from m,α-dichlorotoluene, was attempted but to yiled the desired 10-oxo-2-thia[3,2]metacyclophane. this is attributed to unfavorable geometry in the thiacyclophane due to introduction of the sp2 carbonyl carbon. Two isomeric dioxo-dithia[3,2,3,2]metacyclophanes were however isolated from the coupling reaction. Both there cyclophanes were found to be conformationally higly mobile by variable-temperature NMR studies.
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■ Synthesis of 4-Aminothieno[2,3-c]pyrid-7-one from 4-Aminocyclopenta[b]thiophen-6-one
Patrick Dallemagne, Sylvain Raute, Michel Cugnon de Sévricourt, and Max Robba*
*Laboratorie de Chimie Thérapeutique, U.F.R. des Sciences Pharmaceutiques, 1, rue Vaubénard, 14032 Caen Cedex, France
Abstract
4-Aminothieno[2,3-c]pyrid-7-one derivatives are obtained selectively by ring enlargement of 4-aminocyclopenta[b]thiophen-6-one derivatives using Schmidt or Beckmann rearrangement. Ir and 1H-Nmr spectra are described.
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■ Efficient Conversion of Alkyl Halides to Aldehydes Using Pyrazinylsulfinyl Group
Makoto Shimazaki, Takako Nakanishi, Minoru Mochizuki, and Akihiro Ohta*
*Tokyo University of Pharmacy and Life Science, 1432-1 Horinouchi, Hachioji, Tokyo 192-0392, Japan
Abstract
Reactions of pyrazinyl sulfoxides with trifluoroacetic anhydride and the subsequent treatment with aqueous K2CO3 or NBS gave aldehydes rapidly in excellent yields.
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■ NMR Spectroscopy and X-Ray Crystallography of Benzo[a]quinolizidines
Mario Rubiralta, Anna Diez, Joan Bosch,* Miguel Feriz, and Xavier Solans
*Laboratory of Organic Chemistry, Faculty of Pharmacy, University of Barcelona, Av. de Joan XXIII, s/n, 08028 Barcelona, Spain
Abstract
A series of 9,10-dimethoxy-1,3,4,6,7,11b-hexahydro-2H-benzo[a]quinolizines 1-10 has been studied by nmr spectroscopy using two-dimensional techniques. The crystal structure of benzo-[a]quinolizidines 1 and 4 has been determined by X-ray analysis.
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■ Photochamistry of Conjugated Nitrogen-Carbonyl System. V. Photoisomerization of 3,4-Diazabicyclo[4.2.0]oct-4-en-2-one System
Eisuke Sato, Masato Hasebe, and Yuichi Kanaoka*
*Faculty of Pharmaceutical Sciences, Hokkaido University, Kita 12 Nishi 6, Kita-ku, Sapporo, Hokkaido 060-0812, Japan
Abstract
Irradiation through a Vycor filter of 3,4-diazabicyclo-[4.2.0]oct-4-en-2-ones(3) obtained by photoaddition of 3(2H)-pyridazinones (1) and olefin resulted in isomerization to give 2,3-diazatricyclo-[3.3.0.02,8]octa-4-ones (4).
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■ 1-Functionalized 5,6-Dimethyl-6H-pyrido[4,3-b]carbazoles (Ellipticines) and Analogues: A New Rapid Synthesis
Emile Bisagni,* Marilys Rautureau, and Christiane Huel
*URA 1387 CNRS, Section de Biologie Batiments 110-112, Institut Curie, 15 Rue Georges Clemenceau 91405 Orsay, France
Abstract
4-Acetyl-2-chloro-3-lithlopyridine ethylene glycol ketal reacts with 3- formyl-5-methoxy-1-methylindole and 3-formyl-1-methyl-1H-pyrrol[3,2-c] pyridine, giving the expected alcohols whose triethylsilane-trifluoroacetic acid reduction at room temperature followed by ketal hydrolysis and cyclisation in acidic medium leads in one step to 1-chloro-9-methoxy-5,6-dimethyl-6H-pyrido[4,3-b] carbazole and 10-chloro-5,6-dimethyl-5H-pyrido [3’,4’:4,5] pyrrolo [2,3-g] isoquinoline respectively, in 30 % overall yields. 1-Functionalized 11-nor-ellipticiner and analogues are thus obtained a two-step convergent pathway which appears to be particularly attractive for the rapid synthesis of various condensed heterocyclic systems.
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■ Metalation Reactions. XII. One-pot Synthesis of 1,3-Benzothiasiloles, 1,3-Benzothiastannoles and 1,3-Benzodithioles
Salvatore Cabiddu,* Claudia Fattuoni, Costantino Floris, and Gioanna Gelli
*Istituto di Chimica Organica, Università di Cagliari, Via Ospedale 72, I-09124 Cagliari, Italy
Abstract
The dilithiated species of (methylthio)benzene reacts with various dichlorosilanes, dichlorostannanes and sulfur chloride yielding derivatives of 1,3-benzothiasilole, 1,3-benzothiastannole and 1,3-benzodithiole respectively. By reaction with tetrachlorosilane a spirocyclic silicon compound is obtained. A description of the synthesis is given. The structures of the reaction products were determined by elemental and spectroscopic analyses.
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■ Introduction of Alkyl Groups at the α-Positions of Pyrrolidines and Piperidines: Synthesis of (±)-Coniine
Tatsuo Nagasaka,* Hideki Hayashim and Fumiko Hamaguchi
*School of Pharmacy, Tokyo University of Pharmacy and Life Science, 1432-1 Horinouchi, Hachioji, Tokyo 192-0392, Japan
Abstract
The conversion of lactams to α-alkylated cyclic amines is described. Reactions of α-ethoxyurethanes with trimethylsilyl cyanide in the presence of Levis acid afford the corresponding α-cyanourethanes, which, via carbanion, are alkylated to α-alkyl-α-cyanourethanes in moderate to high yields. Syntheses of (±)-coniine and trans-quinolizidine are carried out as model experiments for dealkoxycarbonylation and decyanation of 2-alkyl-1-alkoxycarbonyl-2-cyanopiperidines.
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■ Synthesis of 3-Amino-4-benzoylsydnones
Wilhelm Fleischhacker* and Ernst Urban
*Institute of Pharmaceutical Chemistry, University of Vienna, Währinger Strasse 10, A-1090 Vienna, Austria
Abstract
In a three step synthesis starting from ethyl hyarazinoacetate HCl (1), 3-benzylidenaminosydnone (4) was available in good yields. Reduction with sodium boranate gave 3-benzylaminosydnone (5a). Lithiation and electrophilic substitution of 5a was studied. Reacting lithiated 5a with N,N-dimethylbenzamide afforded 3-benzylamino-4-benzoylsydnone (5i) which could be deprotected to give 3-amino-4-benzoylsydnone (8b).
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■ Improvements in the Total Synthesis of Physostigmine: Reductive Cyclization of Oxindoles to Tricyclic Indoleninepyrrolidines with Lithium Aluminium Hydride in Tetrahysrofuran
Qian-Sheng Yu and Arnold Brossi*
*Medical Chemistry Section, Laboratory of Chemistry, NIDDK,. National Institute of Health, Bethesda, MD 20892, U.S.A.
Abstract
Reductive cyclization of oxindole 2 and carbamate 5 with LAH in THF afforded the indoleninepyrrolidines 7 and 11 in high yield. The former compound is an important intermediate in our syntheeia of (-)- and (+)-physostigmine (optical isomers of 12). Menthylearbamatee 6 and 9 prepared from 4 and 7 with menthyl chloroformate could not be separated respectively on TCL by standard techniques.
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■ Enantioselective Reduction of Racemic Epoxides with the Chiral 9-Alkoxy-9-borabicyclo[3.3.1]nonane-Potassium Hydride and Chiral Potassium 9-Alkoxy-9-boratabicyclo[3.3.1]nonane Systems
Jin Soon Cha,* Kwang Woo Lee, Mal Sook Yoon, and Jae Cheol Lee
*Department of Chemistry, Yeungnam University, Kyongsan 712-749, Korea
Abstract
The chiral 9-alkoxy-9-borabicyclo[3.3.1]nonane (1 and 2)-potassium hydride and chiral potassium 9-alkoxy-9-boratabicyclo[3.3.1]nonane (3 and 4) systems were applied to the enantioselective reduction (resolution) of representative racemic epoxides, such as 1,2-epoxybutane, 1,2-epoxyoctane, 3,3-dimethyl-1,2-epoxybutane, and styrene oxide. The enantioselectivity by 1-KH and 2-KH systems was in the range of 9.8-46.3% ee. The corresponding chiral borhydrides, 3 and 4, resolved racemic epoxides examined in the range of 9.8-43.3% ee. All the reduction products were consistently enriched in the enantiomer with levoratation.
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■ Hydroltsis of Ketol Trimethylenedithioacetals. Attempted Synthesis of Yashabushiketol
Tse-Lok Ho,* Raymond J. Hill, and C. M. Wong
*Department of Chemistry, University of Manitoba, Winnipeg, Manitoba R3T 2N2, Canada
Abstract
ThaIlium(III) trifluroacetate has been shown to cleave dithianes which contan hydroxy functions that other reagents fail. Hydrolysis of a direct precursor of yashabushiketol led to tetrahydro-γ-pyrones. however.
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■ The Alkylation of MEthyl 2-(1-Pyrrolyl)acetate. A New Synthetic Method of α-Amino Acids
Choji Kashima* and Tatsuya Maruyama
*Department of Chemistry, University of Tsukuba, 1-1-1 Ten-nodai, Tsukuba-shi, Ibaraki, 305-8571, Japan
Abstract
The alkylation of 2-(1-pyrrolyl)acetates was accomplished by the treatment with alkyl halides in the presence of LDA to give 2-(1-pyrrolyl)alkanoates, which were convertible into α-amino acids by ozonolysis.
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■ Preparation of Thiophene Oligomers
Juzo Nakayama,* Toru Konishi, and Masamatsu Hoshino
*Department of Chemistry, Faculty of Science, Saitama University, Saitama, Saitama 338-8570, Japan
Abstract
Thiophene oligomers continue to attract much attention mainly because of their unique biological activities and as starting materials for the preparation of organic conductors. The present review summarizes recent development in synthetic chemistry of oligothiophenes.
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■ Conversion of Beta-Lactams to Versatile Synthons via Molecular Rearrangement and Lactam Cleavage
Maghar S. Manhas,* Dilip R. Wagle, Julian Chiang, and Ajay K. Bose
*Department of Chemistry and Chemical Engineering, Stevens Institute of Technology, Castle Point on the Hudson, Hoboken, NJ 07030, U.S.A.
Abstract
Substituted β-lactams can be synthesized by a variety of methods some of which are stereocontrolled and diastereoselective. Because of their high chemical reactivity and their propensity for molecular rearrangement, these β-lactams can serve as efficient syntnons for racemic or optically active forms of diverse types of natural products such as carbohydrates, alkaloids, amino acids and oligopeptides.