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. 8, 1990
Published online:
■ Triazinobenzothiazine — A New Heterocyclic System via a Novel Cyclization Reaction
John H. Musser,* Susan C. Lewis, and Reinhold H. W. Bender
*Wyeth-Ayerst Research Inc., CN 8000, Princeton, NJ 08543-8000, U.S.A.
Abstract
The synthesis and X-ray structure of 9-chloro-2,4-dimethyl[1,3,5]triazino[2,1-c]-1,4-benzothiazine-1,3(2H,4H)-dione (2) are reported. A mechanism is proposed for the formation of this novel heterocyclic system.
Published online:
■ Regioselective Synthesis of Optically Active (R)-5-Methyl- and (R)-7-Methyl-5,6,7,8-tetrahydroquinolines
Giorgio Chelucci,* Sergio Cossu, Gianfranco Scano, and Francesco Soccolini
*Department of Chemistry, University of Sassari, Via Vienna 2, I-07100 Sassari, Italy
Abstract
Five synthetic routes have been evaluated for the regioselective preparation of (R)-5-methyl- and (R)-7-methyl-5,6,7,8-tetrahydroquinolines from (+)-(R)-3-methylcyclohexanone.
Published online:
■ Furanoeremophilanes from Senecio andreuxii
Benito Reyes and Guillermo Delgado*
*Instituto de Química, Universidad Nacional Autónama de México, Ciudad Universitaria, Circuito Exterior, Coyoacán 04510, Mexico
Abstract
From the leaves of Senecio andreuxii (Compositae) two new furanoermophilanes, 1-deacetyl-6-angeloyl-2,3-deoxy-hilliardinol (1) and 3α-angeloxy-6β-senecioyloxy-10βH-furanoeremophil-9-one (2), and the known 3, were isolated and structurally elucidated.
Published online:
■ Phenolic Compounds from Salix sachalinensis
Mizuo Mizuno,* Masaya Kato, Nobue Hosoi, Munekazu Iinuma, Toshiyuki Tanaka, Akira Kimura, Hiroyoshi Ohashi, Hideki Sakai, and Tadashi Kajita
*Department of Pharmacognosy, Gifu College of Pharmacy, 6-1 Mitahora-higashi 5-chome, Gifu 502-8585, Japan
Abstract
Two new glucosides of phenolic compounds, sachalisides 1 (1) and 2 (2), were isolated from the bark of Salix sachalinensis and their structures were established by the spectroscopic analysis. The aglycone moiety of sachalisdie 2 was a new type skeleton consisting of C6-C3-C6-C3-C6 units (flavan-3-ol substituted with phenylpropanoid on the A-ring).
Published online:
■ Preparation of Newly Modified DIOP Bearing Bis(4-dimethylamino-3,5-dimethylphenyl)phosphino Groups and Its Application to Efficient Asymmetric Hydrogenation of Itaconic Acid Derivatives
Kiyoshi Yoshikawa, Kiyoshi Inoguchi, Toshiaki Morimoto, and Kazuio Achiwa*
*Schol of Pharmaceutical Sciences, University of Shizuoka, 395 Yada, Shizuoka 422-8526, Japan
Abstract
We prepared a modified DIOP analogue bearing bis(4-dimethylamino-3,5-dimethylphenyl)phosphinogroups. Its rhodium complex was found to be a useful catalyst for asymmetric hydrogenation of dimethyl itaconate and itaconic aicd derivatives bearing β-aryl goups.
Published online:
■ I2-Induced Enoletherification of α-Allyl Substituted β-Keto Sulfones; A Route to 3-Phenylsulfonyl-2,5-disubstituted Furans
Jae Wook Lee and Dong Young Oh*
*Korea Advanced Institute of Science and Technology, 373-1, Kusong-Dong, Yusung-Gu, Taejon, Korea
Abstract
Iodine-induced enoletherification of α-allyl substituted β-keto sulfones leads to 4,5-dihydro-5-iodomethylfurans which are readily converted to 3-phenylsulfonyl-2,5-disubstituted furans.
Published online:
■ Rearrangement of Exomethylenecephams to Homocephams
John M. Morin, Jr.,* Douglas O Spry, Thomas K. Elzey, Michael D. Kinnick , Jonathan W. Paschal, and Nancy J. Snyder
*Lilly Reserach Laboratories, Eli Lilly & Company, Lilly Corporate Center, Indianapolis, IN 46285-4813, U.S.A.
Abstract
Exomethylenecephams rearrange by reaction with diazo compounds in the presence of cupric sulfate to generate the homocepham ring-system.
Published online:
■ A New Heterocycle with Analgesic Activity: 2,6-Epoxy-1,2,3,4,5,6-hexahydro-3-methyl-3-benzazocine
Bernhard Wünsch,* Georg Höfner, and Gerd Bauschke
*Institut für Pharmazie und Lebensmittelchemie der Universität München, Sophienstr. 10, 8000 München 2, Germany
Abstract
The title compound (4) was prepared in five steps, starting with the benzaldehyde derivative (5). In the mouse writhing-test 4 showed strong analgesic activity.
Published online:
■ Tandem Michael Addition-[3,3] Sigmatropic Rearrangement Processes — A Concise Route to Functionalized 3-Alkoxycarbonylindoles —
Masahiro Toyota and Keiichiro Fukumoto*
*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan
Abstract
The synthesis of methyl indole-3-carboxylate (4) and methyl 6-methoxyindole 3-carboxylate (7) by tandem Michael addition-[3,3] sigmatropic rearrangement reaction is described.
Published online:
■ Imidazole Derivatives. Part V. Imidazo[1’,2’:1,6]pyrdio[2,3-d]pyridazine: Synthesis, Structure, and Preliminary Chemistry of a Novel Heterocyclic Ring System
Hans-Joachim Knökler,* Roland Boses, and Rainer Hitzemann
*Institut für Organische Chemie, Universität Hannover, Schneiderberg 1 B, D-30167 Hannover, Germany
Abstract
Reaction of functionalized imidazo[1,2-a]pyridines with hydrazine hydrate to the novel imidazo[1’,2’:1,6]pyrido[2,3-d]pyridazine ring system is described.
Published online:
■ Pentacyclic Indole Alkaliods: A Short Synthesis of (±)-N(a)-Benzyl-20-desethylaspidospermidine
Daniel Gardette, Jean-Claude Gramain,* and Marie-Eve Sinibaldi
*Chimie des Substances Naturelles, URA 485 CNRS, Université Blaise Pascal (Clermont II), 63177 Aubière Cedex, France
Abstract
The synthesis of (±)-N(a)-benzyl-20-desethylaspidospermidine in 8 steps and 25% overall yield from cyclohexanedione is described.
Published online:
■ The [3+2] Intramolecular Cycloaddition Reaction of Azomethine Ylides Generated from Benzylic N-Oxides
Georges Roussi
*Institut des Chimie des Substances Naturelles, C.N.R.S., 1 avenue de la Terrasse, Bat. 27, 91198 Gif-sur-Yvette Cedex, France
Abstract
Benzylic azomethine ylides (Y) generated by deprotonation of the corresponding tertiary amine N-oxides (1a, 1b, 4) react intramolecularly with the suitably positioned unactivated double bond to yield the corresponding fused membered pyrrolidines (2a, 2b, 5). A competitive evolution of the ylide is observed at low temperature leading to the corresponding head to head piperazines (3, 6, 8).
Published online:
■ N-[2(1H)-Perimidinylmethyl]azinium Salts. Their Synthesis and Reaction with Electrophiles
Andrés Molina, Ana M. Cuadro, Julio Alvarez-Builla,* Juan J. Vaquero, and José L. Garcia Navio
*Departamento de Química Orgánica, Universidad de Alcalá de Henares, 28871 Alcalá de Henares (Madrid), Spain
Abstract
A synthesis of new 2-substituted 1H-perimidines by the reaction of 1-[(methylthio)thiocarbonylmethyl]azinium salts and 1,8-diaminonaphthalene is described. Reaction of these perimidine derivatives with several electrophiles is also reported.
Published online:
■ The Reaction of 8-Methylpyrrolo[1,2-a]pyrazines with Dimethyl Acetylenedicarboxylate
Paul V. S. Kong Thoo Lin,* Robert Buchan, Martin Fraser, and Derek McHattie
*MRC, Labratory of Molecular Biology, Hills Road, Cambridge, CB2 2QH, U.K.
Abstract
2,8-Dimethylpyrrolo[1,2-a]pyrazine reacts with two molecular proportions of dimethyl acetylenedicarboxylate (DMAD) in toluene to give a reaction mixture from which five crystalline products were isolated. Four of the products were shown to be the isomeric tetracarbomethoxy 1:2 addcuts (9, 10, 14 and 15) and the fifth to be the tricarbomethoxydipyrrolopyrazine (7). A likely common reaction intermediate leading to the formation of all five products is suggested to be the 1:1 adduc (21). Reaction of 2,3,8-trimethylpyrroo[1,2-a]pyrazine with DMAD in toluene gave the corresponding compounds (17, 18, 19, 20 and 16).
Published online:
■ Isonoyaine, a New C-Ring Secocularine Alkaloid
Olga Blanco, Luis Castedo,* Diego Cortes, and M. Carmen Villaverde
*Departamento de Química Orgánica, Facultad de Química, Universidad de Santiago de Compostela, E-15706, Santiago de Compostela, Spain
Abstract
We report the isolation of isonoyaine (1), a new C-ring secocularine alkaloid, from Sarcocapnos saetabensis. Its structure was established on the basis of its spectroscopic data and confirmed by total synthesis
Published online:
■ Synthesis of Aspidosperma Alkaloids: Eight-membered vs. Six-membered Ring D Formatnion
Monique Dufour, Jean-Claude Gramain,* Henri-Philippe Husson, Marie-Eve Sinibaldi, and Yves Troin
*Chimie des Substances Naturelles, URA 485 CNRS, Université Blaise Pascal, 63177 Aubière Cedex, France
Abstract
Unusual cyclization of the acetyl chain borne at C-20 of a tetracyclic intermediate (11a) or (11b) led to the formation of a pentacyclic analog of aspidosperma alkaloids with an eigth-membered ring D.
Published online:
■ Synthesis of Nectriafurone, an Isofuranonaphthoquinone Isolated from the Fungus Nectria haematococca
Michel Devys, Michel Barbier,* and Denise Parisot
*Institut des Chimie des Substances Naturelles, C.N.R.S., 1 avenue de la Terrasse, Bat. 27, 91198 Gif-sur-Yvette Cedex, France
Abstract
Synthesis of 5-methoxy-4,7-dihydroxynaphtho[2,3-c]8,9-furandione (2) and of 4,7-dihydroxynaphtho[2,3-c]8,9-furandione (3) were carried out by a rapid Friedel-Crafts reaction using the dry method. The addition of acetaldehyde on 2 in presence fo LDA gave the (±)-nectriafurone (1), thus cofirming the proposed structure of 3-(1‘-hydroxyethyl)-5-methoxy-4,7-dihydroxynaphtho[2,3-c]8,9-furandione.
Published online:
■ Reaction of Azepines with Palladium (II) Acetate: Formation of Mucondialdehyde and Dihydroazepine Derivative
Katsuhiro Saito,* Masatoshi Kozaki, and Kensuke Takahashi
*Department of Applied Chemistry, Nagoya Institute of Technology, Gokiso-cho, Showa-ku, Nagoya 466, Japan
Abstract
Reaction of 1-carboethoxy-1H-azepine with palladium (II) acetate in chloroform or acetonitrile afforded trans-trans-mucodialdehyde together with ethyl carbamate. On the other hand, the analogous reaction in acetic acid gave 1-carboethoxy-2,3-diacetoxy-2,3-dihydro-1H-azepine. The same reaction but using 1-carboethoxy-1H-1,2-diazepine gave a nitrile derivative via a ring opening.
Published online:
■ Synthesis of Some Conformationally Restricted Analogs of Serotonin
John E. Macor* and Kevin Ryan
*Department of Medical Chemistry, Central Research Division, Pfizer Inc., Groton, Connecticut 06355, U.S.A.
Abstract
3-(2-Aminocycloalkyl)-5-methoxyindoles (3) have been synthesiezed via a three setp procedure starting with 5-methoxyindole. These molecules represent conformationally restricted analogs of serotonin.
Published online:
■ Palladium-catalyzed Reaction of 3-Bromoindole Derivative with Allyl Esters in the Presence fo Hexa-n-butyldistannane
Yuusaku Yokoyama, Masato Ikeda, Masaaki Saito, Tomoko Yoda, Hideharu Suzuki, and Yasuoki Murakami*
*School of Pharmaceutical Sciences, Toho University, 2-2-1, Miyama, Funabashi, Chiba 274-8510, Japan
Abstract
The palladium-catalyzed cross-coupling reaction of ethyl 3-bromo-1-tosylindole-2-carboxylate (9) with a variety of substituted allylic acetates or carbonates (10) in the presence of hexa-n-butyldistannane (6) gave 3-allylated indoles (11) in high yields.
Published online:
■ Deuterioformylation by the Oxonolysis of 2-Deuterio-5-phenyl- or 5-Deuterio-2-phenyloxazoles
Choji Kashima* and Hideki Arao
*Department of Chemistry, University of Tsukuba, 1-1-1 Ten-nodai, Tsukuba-shi, Ibaraki, 305-8571, Japan
Abstract
The oxonolysis of 5-deuterio-2-phenyloxazole (1b) gave deuterioformic benzoic anhydride (3b) and N-formylbenzamide (4). The reaction of the ozonolysate of 1b with various nucleophiles is not practical due to the formation of 4. Since 2-deuterio-5-phenyloxazole (2b) gave 3b quantitatively under the same conditions, the ozonolysis of 2b is concluded to be a more practical and convenient preparation of the deuterioformylating agents.
Published online:
■ Studies on the Alkaloids from Aconitum contortum (I)
Kazuaki Niitsu,* Yukinobu Ikeya, Hiroshi Mitsuhashi, Chen Siying, and Liang Huiling
*Research Institute for Biology & Chemistry, Tsumura & Co., 3586 Yoshiwara, Ami-machi, Inashiki-gun, Ibaraki, 300-11, Japan
Abstract
A new diterpenoid alkaloid, contortumine (1), and seven known diterpenoid alkaloids were isolated from the roots of Aconitum contortum. Structures of these alkaloids were determined on the basis of spectral and chemical data.
Published online:
■ Asymmetric Synthesis of (+)- and (-)-Coniines and (-)-Sedamine by Diastereoselective Alkylation Reaction of Ethoxypiperidinone
Toshiko Kiguchi, Yoko Nakazono, Sanae Kotera, Ichiya Ninomiya, and Takeaki Naito*
*Kobe Women’s College of Pharmacy, Motoyamakita, Higashinada, Kobe 658, Japan
Abstract
Diastereoselective alkylation reaction of the chiral 6-ethoxypiperidinoes (4) and (5) has been developed and successfully applied to the asymmetric synthesis of piperidine alkaloids, (+)- and (-)-coniines (11) and (12), (-)-sedamine (21), and (-)-allosedamine (22).
Published online:
■ A New Synthesis of 5,6-Dihydro-4H-1,3,4-thiadiazine 1,1-Dioxides from Methyl Styrylsulfonylacetate
Masahiko Takahashi* and Ichiro Yamashita
*Department of Industrial Chemistry, Faculty of Engineering, Ibaraki University, 4-12-1 Nakanarusawamachi, Hitachi, Ibaraki 316-8511, Japan
Abstract
Treatment of methyl styrylsulfonylacetate with arenediazonium chloirdes gave methyl styrylsulfonylglyoxylate arenehydrazones, which were cyclized on treatment with bases to 4-aryl-5-phenyl-5,6-dihydro-1,3,4-thiadiazine 1,1-dioxides, a hitherto unknown class of heterocycles.
Published online:
■ Stereoselective Synthesis of 1-Indanylidene Substituted Heteroaromatic Derivatives via Pd-catalyzed Tandem Insertion and Cross Coupling Reactions
Fen-Tair Luo* and Ren-Tzong Wang
*Institutue of Chemistry, Academia Sinica, 128, Yan-Chiu-Yuan Road, Sec II, Nankang, Taipei,11529, Taiwan, R.O.C.
Abstract
Treatment of 4-(o-iodophenyl)-1-butyne with a variety of heteroarylzinc chlorides in the presence of a catalytic amount of Pd(PPh3)4 gave (Z)-1-indanylidene substituted heteroaromatics in moderate to good yields with high Z-selectivities.
Published online:
■ A Practical Approach to the Synthesis of 1,2,3,4,6,7,8,9-Octahydro-1,3-dimethylprimido[2,1-f]purine-2,4,8-trione
Vivekanand Kamath, Jahangir, and David C. Baker*
*Department of Chemistry, University of Alabama, Box 870336, University, Tuscaloosa, Alabama 35478-0336, U.S.A.
Abstract
A practical synthesis of 1,2,3,4,6,7,8,9-octahydro-1,3-dimethylpyrimido[2,1-f]purine-2,4,8-trione, which obviates difficulties encountered in exeuting th epublisehd method, is described.
Published online:
■ Practical Route to Both (S)- and (R)-Enantiomers of O-(4-Methoxyphenyl)glycidol Using (S)-1,2-O-Isopropylideneglycerol as a Common Precursor
Seiichi Takano,* Minoru Moriya, Mahito Suzuki, Yoshiharu Iwabuchi, Takumichi Sugihara, and Kunio Ogasawara
*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan
Abstract
Practical route to both (R)- and (S)-enantiomers of O-(4-methoxyphenyl)glycidol is devised using (S)-1,2-O-isopropylideneglycerol as a common chiral starting material.