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. 1, 1988
Published online:
■ Diterpenoid Alkaloids from Delphinium peregrinum. The Structure of Peregrine
Gabriel de la Fuente,* José A. Gavín, Rafael Díaz Acosta, and José A. Morales
*Instituto de QUímica Orgánica, Instituto de Productos Naturales Orgánicos, Instituto de Productos Naturales Orgánicos, La Laguna, Tenerife, Canary Islands, Spain
Abstract
From Delphinium peregrinum var. elongatum Boiss.,bicoloridine, dihydrogadesine, nudicaulidine, 13-acetylhetisinone, and a new C-19 diterpenoid alkaloid peregrine were isolated. The structure of the new base was determined from chemical and spectral evidence.
Published online:
■ Cyclosdditions with Acylhydrazones. Selective Diastereomeric Pyrazolidine Synthesis and Nitrile Acylimine Synthons
Mohamed A. Badawy, Said A. El-Bahaie, Azza M. Kadry, and Yehia A. Ibrahim*
*Department of Chemistry, Faculty of Science, University of Cairo, Giza, Egypt
Abstract
Arylaldehydes N-acylhydrazones 1 undergo dipolar cycloadditions to N-arylmaleimides 2 to give two diasteromeric kinetic and thermodynamic pyrazolidines 3 and 4. Oxidation of 3 and 4 gave the corresponding pyrazolines 5 which were also obtained directly from compounds 1 and 2 in nitrobenzene. The present investigation offers an easy access to nitfile acylimine synthons 6.
Published online:
■ Sodium Borohydride Desulphurization of Thiolactams to Amines
Sukhendu B. Mandal, Venkatachalm S. Glrl, and Satyesh C. Pakrashi*
*Indian Institute of Chemical Biology, Calcutta-700 032, India
Abstract
Sodium borohydride desulphurizes a variety of thiolactams(1-8) in t-butanol/methanol mixture under reflux to the respective amines (9-16) in good yield.
Published online:
■ Direct Thiation of 7-Theophyline Nucleosides
Rodrigo Rico-Gómez,* Manuel L. Ruiz-Mora, Ezequiel P. de Inestrosa Villatoro, and Josefa Rios-Ruiz
*Deparament de Bioquimica, Biologai Molecular y Quimica Orgánica, Universidad de Málaga, 29071 Málaga, Spain
Abstract
8-Methyl-6-thiotheophylline nucleosides have been obtained by treatment of the corresponding 8-methyl-theophylline nucleosides with Lawesson’s Reagent.
Published online:
■ High Regio- and Stereoselective Cycloaddition of a Nitrone to Alkylidenecyclopropanes
Alberto Brandi,* Silvio Carli, and Andrea Goti
*CNR, Centro di Studio Sulla Chimica e la Struttura dei Composti Eterociclici e lolo Applicazioni, c/o Dipartimento di Chimica Organica "Ugo Schiff", Università di Firenze, Via Gino Capponi 9, I-50121 Firenze, Italy
Abstract
The 1,3-dipolar cycloaddition of 5,5-dimethylpyrroline-N-oxide (DMPO) 3 to methylenecyclopropanes substituted on the exocyclic double bond gives exclusively 4-spirocyclopropane isoxazolines when the substituent is aryl or alkyl group, 5-spirocyclopropane iaoxazolines when the substituent is an electron-withdrawing group. This cyclic nitrone gives cycloadducts with high diastereoselectivity.
Published online:
■ Highly Stereoselective Cyclization of Epoxyketone Promoted by Acid
Toshio Suzuki,* Etsuko Sato, Hitomi Ihara, Katsuo Unno, and Tetsuji Kametani*
*Hoshi University, 2-4-41 Ebara, Shinagawa-ku, Tokyo 142-8501, Japan
Abstract
Epoxidation of the protected ally1 alcohol (8) with m-chloroperbenzoic acid provided the unexpected 1-oxa-bicyclo[3.2.03,6]heptane (11) along with the corresponding epoxyketone (10) which was easily converted to (11) by acid.
Published online:
■ A Novel Triflate Mediated Approach to Alkaloidal Glycosides
Zaheer Ahmad, Najam-ul-Hussain Kazmi, Abdul Qasim Khan, and Abdul Malik*
*H. E. J. Postgraduate Institute of Chemistry, University of Karachi, Karachi-75270, Pakistan
Abstract
A mild one pot synthesis of alkaloidal glycosides is reported. In the reaction sequence, classical SN2 displacement of the trifluoromethanesulfonyloxy group in sugar triflate (1) was affected with nucleophilic nitrogen of a variety of naturally occurring alkaloidal bases (2-10) affording alkaloidal N-glycoeides (11-9). Deprotection of the sugar moiety in (11)(18) end (19) with boron trichloride afforded the deprotected compounds (20-22). The strategy provides s general method for the preparation of pharmacologically interesting compounds from readily accessible precursors.
Published online:
■ Chemistry of the 5:7-Fused Heteroaromatic Systems: A Novel Rearrangement Involving the Imidao[4,5-e][1,3,4]triazepine and Pyrazolo[3,4-e][1,3,4]triazapine Systems
Ramachandra S. Hosmane* and Benjamin B. Lim
*Labratorl for Chamical Dynamics, Department of Chemistry, University of Maryland Baltimore County, Catonsville, Maryland 21228, U.S.A.
Abstract
A novel rearrangement which involves the potential intermediacy of an imidazo[4,5-e]- or a pyrazolo[3,4-e][1,3,4]triazepine is reported.
Published online:
■ Two New Oxazoles from Amyris texana P. Wilson
Xorge A. Domínguez, Gabriel de la Fuente,* Antonio G. González, Matís Reina, and Isabel Timón
*Instituto de QUímica Orgánica, Instituto de Productos Naturales Orgánicos, C. S. I. C./ Unversidad de La Laguna, La Laguna, Tenerife, Canary Islands, Spain
Abstract
From the roots of Amyris texana P. Wilson, two new oxazoles, texamine (1) and texaline (2) were isolated together with 0-isopentenylhalfordinol (3). The structures of the new compounds were established by spectroscopic methods, including long-range HETCOR 2-D nmr.
Published online:
■ Procumbine, a New Secoberbine Alkaloid
Eva Táborksá, Frantisek Vezník, Jirí Slavik, Petr Sedmera, and Vilím Simánek
*Institute of Medical Chemistry, Palacky University, 3, Hnevotínská, 775 15 Olomouc, Czech Republic
Abstract
The structure determination of the secoberbine alkaloid procumbine (2) isolated from Hypecoum procumbens and H. leptocarpum is reported.
Published online:
■ Synthetic Approach to the Ivermectin Bottom Half Using Internal Cycloadducts of N-Furfuryl Acrylamides: Functionality and Optical Activity
Michael E. Jung* and Leslie J. Street
*Department of Chamistry and Biochemistry, University of California Los Angeles, Los Angels CA 90024, U.S.A.
Abstract
The 2-(α-benzyloxyacetyl) furan 2b is converted into the aminal 3b which undergoes intemal cycloaddition to give a highly oxidized intermediate 5b in a potential route to ivermectin 1, while the use of (S)-valinol in this sequence permits the ready preparation-separation of both enantiomers of 5a.
Published online:
■ 2-(Heteroatom-substituted)methyl Penems. II. Sulphinyl and Sulphonyl Derivatives
Marco Alpegiani, Ettore Perrone, and Giovanni Franceschi
*Farmitalia Carlo Erba R&D, Via dei Gracchi 35, 20146 Milano, Italy
Abstract
Thermodynamic control of the endo-exo double bond equilibration in 2-(thiosubstituted) methyl penems allowed the synthesis of the sulphinyl and sulphonyl derivatives, which proved to be potent antibacter~al agents.
Published online:
■ A New Intermediated for Methyl Jasmonate and PG‘s from Iridoid Glucoside Aucubin
Enrico Davini, Carlo Iavarone, 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
A synthetic approach to biologically active cyclopentanoids or their intermediates starting from natural heterocyclic precursors (iridoid glucosides) has been devised. Aucubin 1 was efficiently converted into chiral cyclopentenone 9 ,intermediate for synthesis of methyl jasmonate-type compounds and prostaglandins.
Published online:
■ Ptactical Synthesis of Nojirimycin
Yoshisuke Tsuda,* Yukihiro Okuno, and Kimihiro Kanemitsu
*Faculty of Pharmaceutical Scicences, Kanazawa University, 13-1 Takara-machi, Kanazawa 920-0934, Japan
Abstract
The short step and efficient synthesis of nojirimycin (1) from commercially available 1,2-isopropylidene-D-glucofuranose (2) was described. Oxidation of 2 with (Bu3Sn)2O-Br2 followed by oximation, isomerization, and stereoselective reduction gave the 5-amino derivative of glucoconfiguration (6a), which was converted to nojirimycin bisulfite adduct (8) in 50% overall isolated yield.
Published online:
■ Novel Aldol-type Reaction Utilizing 3-Methyl-2-phenyl-2-(2-oxoalkyl)benzothiazoline as an Enolate Transferring Reagent
Hidenori Chikashita,* Shi-ichiro Tame, and Kazuyoshi Itoh
*Department of Applied Chemistry, Faculty of Engineering, Kansai University, Suita, Osaka 564-8680, Japan
Abstract
An enolate transfer-type aldol reaction of the title benzothiazoline with aldehydes was successfully achieved in the presence of SnCl4 to afford the cross aldol products.
Published online:
■ Facile Synthesis of Alcyclic Nucleosides Using a New Coupling Agent of Zinc Iodide
Yong Hae Kim* and Joong Young Kim
*Department of Chemistry, Korea Advanced Institute of Science and Technology, 373-1, Kusung-Dong, Yusung-Gu, Taejon, 305-701, Korea
Abstract
((1,3-Bis(benzyloxy)-2-propoxy)methyl)-2-thiopyrimidine-, uracil-, 2-thiouracil-, and 2-thioadenine- acyclic nucleosides and (2-acetoxyethoxy methyl)-2-thioadenine-, 2-thiopyrimidine-, uracil-, and 2 -thiouracil-acyclic nucleosides have been successfully synthesized in good yields by N-alkylation using a new Lewis acid, zinc iodide in dimethylformamide.
Published online:
■ Absolute Configuration of Kuwanon L, a Natural Diels-Alder Type Adduct from the Morus Root Bark
Yoshio Hano, Shinkichi Suzuko, Hideaki Kohno, and Taro Nomura*
*Faculty of Pharmaceutical Sciences, Toho University, 2-2-1, Miyama, Funabashi, Chiba 274-8510, Japan
Abstract
The absolute configuration of kuwanon L (1) isolated from the Morus root bark (Morus alba L., Moraceae) was determined as 2S, 3”R, 4”R, 5”S by circular dichroism (CD) spectroscopic study.
Published online:
■ Isolation and Structure of New Pseudoguaianolides, 4-Epipulchellin and 4-Epineopulchellin from Gaillardia Pulchella
Kenzo Hariyama, Hitoshi Hori, Tamiko Ohkura, Takeshi Kawamata, Ji-Fu Gao, and Seiichi Inayama*
*Pharmaceutical Institute, School of Medicine, Keio University, Shinanomachi 35, Shinjuku, Tokyo 160-0016, Japan
Abstract
The structure of 4-epipulchellin (1a) and 4-epineopulchellin (1b), new pseudoguaianolide sesquiterpene lactones isolated from Gaillardia pulchella, was determined on the basis of spectroscopic data and chemical transformations from pulchellin (2a) and neopulchellin (2b) into 1a and 1b, respectively.
Published online:
■ Papillamidine - A New Steroidal Alkaloid from the Leaves of Buxus papillosa
Atta-ur-Rahman,* Muzaffar Alam, Gulzar Ahmed, and Muhammad Iqbal Choudhary
*H. E. J. Postgraduate Institute of Chemistry, University of Karachi, Karachi-75270, Pakistan
Abstract
A new steroidal alkaloid, papillamidine, has been isolated from the leaves of Buxus papillosa, to which structure 1 has been assigned.
Published online:
■ Synthesisabd Characerization of Isomeric 2,3,3a,4-Tetrahydro-1H-pyrrolo[1,2-a]benzimidazol-1-ones from 1,2-Phenylenediamines and 3-Acylpropionic Acids
Alba Chimirri, Silvana Grasso, Pietro Monforte, Giobanni Romeo, and Maria Zappalà
*Dipartimento Farmaco-Chimico, Università di Messina, Viale Annunziata, 98168 Messina, Italy
Abstract
Synthesis and identification of isomeric 2,3,3a,4-tetrahydro-1H-pyrrolo[1,2-a]benzimidarol-1-ones are described. A mechanism for their formation is suggested by evaluating the effects of substituents on the phenylenediamine ring in the reaction of 1,2-phenylenediamines and-3-acylpropionic acid. The structures of obtained adducts have bean assigned by means of 1H nmr spectra assisted by NOE measurements.
Published online:
■ Daturilinol - A New Withanolide from the Leaves of Datura metal
Tariq Mahmood, S. Salman Ahmad, and Salimuzzaman Siddiqui
*H. E. J. Postgraduate Institute of Chemistry, University of Karachi, Karachi-75270, Pakistan
Abstract
A withanolide daturilinal (1) has been isolated from the fresh leaves of Datura metel and its structure elucidated through spectral studies.
Published online:
■ Studies on the Synthesis of Heterocyclic Compounds. Part XII. Pyrazolo[4,3-c]-1,5-banzodiazocine-4,10-dione. A New Ring System
Salvatore Plescia,* Maria Luisa Bajardi, Giuseppe Daidone, and Angela Roccaro
*Dipartimento di Chimica e Tecnologie Farmaceutiche, Università degli Studi di Palermo , Via Archirafi n 32 90123 Palermo, Italy
Abstract
Treatment of N-(1-R-4-carboxypyrazol-5-yl)-2-aminobenzamides 2b,e with thionyl chloride afforded new pyrazolo[3,4-d]-1,3-oxazinones 3b,e. When the amide group of compounds 2b,e was blocked pyrazolo[4,3-c]-1,5-benzodiazocine-4,10-diones 6a,d were obtained.
Published online:
■ Photochemistry of Pyridine N-Oxides. Trapping of an Intermediate with Amines
Angelo Albini, Elisa Fasani, and Christian Lohse
*Department o f Organic Chemistry, University of Pavia, Via Taramelli 10, 27100 Pavia, Italy
Abstract
The photochemistry of pyridine N-oxide (1a) and the corresponding 4-benzyl (1b),4-phenyl (1c), and 2,6-dimethyl (1d) derivatives has been investigated or reinvestigated. Substrates 1a and 1b yield a small amount of the corresponding 2-acylpyrroles (5a,b) as the only isolable product. 1d yields 5d in moderate yield and 1c yield 5c in aprotic and the 2-pyridone 7c in protic solvents. In the presence o f diethylamine isomeric 5-diethylaminopentadienenitriles (3,4) are obtained in moderate yield along with deoxygenated pyridines (6). Under this condition no 5 is formed, but the yield of 7 is unchanged. These reactions are most economically accounted for by admitting that nitrene 11 is formed as an intermediate and undergoes rearrangement to pyrroles 5 or polymerization to tars, or it can be trapped by amines (proton abstraction followed by nucleophilic substitution) to yield products 3 and 4. The lactams 7 arise directly from the N-oxide singlet excited state, which is also involved in the deoxygenation by amines.
Published online:
■ Steteoselective Synthesis of Unsaturated Oxetanes
Alexandre Feigenbaum,* Jean-Pierre Pete, and Anne-Lise Poquet-Dhimane
*Laboratoire de Photochimie, U.A. CNRS n°459, UFR Sciences, 51062 Reims, France
Abstract
Butynones 1 and 7 add on alkenes under UV irradiation to afford α-alkynylaretones. The oxetanes obtained with cyclic alkenes have been shown to hove the triple bond endo. Adducts with furan have been converted to an α-vinyloxetane 6 having the double bond endo.
Published online:
■ Photocyclisation of Keto-lactams. A New Synthesis of Functionalized 1-Azabicyclo(x.y.o)alkanes
Assia Azzouzi, Moniquw Dufour, Jean-Claude Gramain,* and Roland Remuson
*Laboratoire de Chimie et Biochimie des Substances Naturtelles, U.A. C.N.R.S., Université de Clermont II, Université de Clermont II, France
Abstract
A series of 1-azabicyclo(x.y.o)alkanes has been synthesized using an intramolecular photoreduction reaction. The methodolgy consists of a regioselective abstraction of an hydrogen α to the nitrogen of an amide by the triplet T1(n,π*) of a carbonyl derivative.
Published online:
■ Effect of Metal Ions in Organic Synthesis. XXXVI. One-pot Synthesis of New 3-Carbonyl- and 3-Carbonyl-N-phosphorus-1-aminopyrroles
Orazio A. Attanasi,* Paolino Filippone, Paola Guerra, and Franco Serra-Zanetti
*Istituto di Chimica Organica , Facolta di Scienze, Università di Urbino, Piazza della Repubblica 13, I-61029 Urbino, Italy
Abstract
The one-pot synthesis of a lot of - new 3-carbonyl-N-phasphorus-1-aminopyrroles and 3-carboxy-N-phosphorus-1-aminopyrroles by reaction of some N-phosphinic and N-phusphonic conjugated azoalkenes with β-diketones and β-ketoesters is reported. A different role played in these reactions by copper(II) chloride catalyst was also observed.
Published online:
■ Reaction of 1,4-Diaza-1,3-butadienes with Cyanotrimethylsilane. Synthesis of 2,3-Bis(arylamino)propenenitriles and Their Cyclization to 1,4-Diaryl-2,3-dioxo-5-pyrazinecarbonitriles
Masahiko Takahashi,* Hiroaki Miyahara, and Noriyuki Yoshida
*Department of Materials Sciences, Faculty of Engineering, Ibaraki University, 4-12-1 Nakanarusawamachi, Hitachi, Ibaraki 316-8511, Japan
Abstract
Reaction of 1,4-diaza-1,3-butadienes (1) with cyanotrimethylsilane gave 2,3-bis(arylamino)propenenitriles (4), which were cyclized to 1,4-diaryl-2,3-dioxo-5-pyrazinecarbonitriles (5) on treatment with oxalyl chloride. The propenenitriles (4) were oxidized by oxygen to 2,3-bis(arylimino)- propanenitriles (7) , which were chlorinated with thionyl chloride to yield 2,3-bis(ary1imino)-3-chloropropropanenitril (9).
Published online:
■ Carbodiimide-mediated Annelation of a [1,2,4]Triazole Ring into a Heterocyclic Ring: Synthesis of [1,2,4]Triazolo[4,3-b]triazole, Imidazo[1,2-b][1,2,4]triazole and [1,2,4]Triazolo[1,5-d][1,2,4]triazine Derivatives
Pedro Molina,* Mateo Alajarín, Alicia Ferao, Angeles Lorenzo, Ma Jesús Vilaplana, Enrique Aller, and José Planes
*Departmento de Química Orgánica, Facultad de Ciencias, Universidad de Murcia, 30071 Murcia, Spain
Abstract
The N-aminoazoles 1 and 4 react with diarylcarbdiimides to give the corresponding N-guanidinoazoles which undergo base-catalyzed cyclization to give the fused [1,2,4]triazoles 3 and 6 respectively.The reactions of N-aminotriazines 7 and 8 with diarylcarbodzimides lead directly to the new triazolo-trlazines 9 which display mesoionic character.
Published online:
■ Pseudoesters and Derivatives. XXVIII. The Reaction of 5-Methoxy-3-pyrrolin-2-one and Its 3-Bromo Derivative with Nitrogen and Sulphur Nucleophiles
M. Dolores Jiménez, Raquel Ortega, Amelia Tito, and Francisco Fariña*
*Instituto de Química Orgánica General, C. S. I. C., Calle Juan de Cierva, 3, 28006 Madrid, Spain
Abstract
5-Methoxy-3-pyrrolin-2-one (1) reacts with dimethylamine yielding the corresponding conjugate addition product 3a. By using pyrrolidine, piperidine and diethylamine the addition product 3 is accompanied by the 5-dialkylamino-5-pytrolin-2-one 4, which in the latter case is the main component. Similar results are obtained with 3-bromo-5-methoxy-3-pyrrolin-2-one (2) and the afore-mentioned amines. The reaction of 1 and 2 with thiois under basic catalysis gives only the conjugate addition products 7 and 13 respectively.
Published online:
■ Hetisine Derivatives, Part 1: Acetylation and Oxidation of Hetisine
Jan A. Glinski, Balawant S. Joshi, Quing Ping Jiang, and S. William Pelletier*
*Department of Chemistry, Institute for Natural Products Research, The University of Georgia, Chemistry Building, Athens, Georgia 30602-2556, U.S.A.
Abstract
Acetylation of hetisine (1) under drastic conditions afforded 2-acetyl (8), 11-acetyl (9), 13-acetyl (5), 2,11-diacetyl (7), 11,13-diacetyl (2) and 2,11,13-triacetyl (6) hetisines. Sarett oxidation of the compounds (9), (5), (7) and (2) gave 11-acetyl-2,13-didehydro (11), 13-acetyl-2,11-didehydro (12), 13-dehydro-2,11-diacetyl (14) and 2-dehydro-11,13-diacetyl (10) hetisines, respectivsly. Alkaline hydrolysis of (12) and (8) gave 2,11-didehydrohetisine (13) and 2-dehydrohetisine (hetisinone) (3), respectively. Sarett oxidation of hetisine (1) afforded (13) as the major product besides 11-dahylrohetisine (15). All the compounds have been characterized by their ir, ms, 1H nmr and 13H nmr data. The location of keto groups in the hetisine derivatives (3), (10), (11), (12), (13), (14) and (15) has been confirmed by CD and ORD meaeurements.