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. 45, No. 5, 1997
Published online:
■ C2-Alkylaminopenem Synthesis
Takumi Yamasaki, Hiroshi Kadoi, and Isao Nagakura*
*Chemical Process Development Laboratory, Drug Substance Manufacturing Plant, Pfizer Pharmaceuticals, 5-Gochi, Taketoyo-cho, Chita-gun, Aichi, Japan
Abstract
A simple synthesis of C2-dialkylaminopenems is described. Azetidione glyoxylate has been cyclized to C2-aminopenem, via an intramolecular sulfide-contraction reaction.
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■ Convenient Preparation of 1-Azaazulene Derivatives by the Reaction of Tropon-imines with Enamines
Makoto Nitta* and Tohru Takayasu
*Department of Chemistry, School of Science and Engineering, Waseda University, 3-4-1 Okubo, Shinjuku-ku, Tokyo 169-8555, Japan
Abstract
Troponimines having OH, OMe, OMs, and OTs group on the nitrogen atom react with pyrrolidine enamines to give formal [8+2] cycloadducts, which undergo spontaneous aromatization to give 1-azaazulene derivatives in good to moderate yield.
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■ Novel Cyclizatoin of Unsaturated Alcohols by Phenyl Selenocyanate in the Presence of Copper Bis-(trifluoromethanesulfonate)
Hirofumi Inoue and Shizuaki Murata*
*Graduate School of Human Informatics, Nagoya University, Nagoya 464-8601, Japan
Abstract
Intramolecular oxyselenenylation of unsaturated alcohols by phenyl selenocyanate with copper bis(trifluoromethanesulfonate) proceeds stereoselectively to give cyclic ethers.
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■ Novel Heterocyclic Enediynes. Molecular Design, Chemical Synthesis and DNA Cleavage
Kazunobu Toshima,* Kiyoshi Ohishi, Miho Tomishima, and Shuichi Matsumura
*Department of Applied Chemistry, Faculty of Science and Technology, Keio University, Hiyoshi, Kohoku-ku Yokohama 223-8522, Japan
Abstract
The novel 10-membered oxaenediyne (4a) and azaenediynes (5a-d) were designed and synthesized in a short procedure, and the azaenediynes (5a-d) were found to effectively cleave DNA under both weakly acidic and basic conditions with no additive.
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■ Imidazo[4,5-e][1,2,4]triazocine: A Novel 5:8-Fused Ring System Riddled With Rearrangements
Friedrick N. Burnett and Ramachandra S. Hosmane*
*Laboratory for Drug Design and Synthesis, Department of Chemistry and Biochemistry, University of Maryland Baltimore County, 1000 Hilltop Circle, Baltimore, Maryland 21228, U.S.A.
Abstract
Attempts to synthesize the title 5:8-fused heterocyclic ring system resulted in a number of novel opportunistic rearrangements and transformations. There is, however, some evidence to believe that one of these rearrangements might proceed through the transient intermediacy of this ring system.
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■ Triethylborane-mediated Atom Transfer Cyclization of N-Allylic α-Iodo-acetamides: A Convenient Synthesis of β-Iodomethyl-γ-lactams
Masazumi Ikeda, Hirotaka Teranishi, Noriko Iwamura, and Hiroyuki Ishibashi*
*Faculty of Pharmaceutical Scicences, Kanazawa University, 13-1 Takara-machi, Kanazawa 920-0934, Japan
Abstract
In the presence of triethylborane, N-allylic α-iodoacetamides underwent atom tranfer cyclization to give β-iodomethyl-γ-lactams in high yields.
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■ Revised Structure of Sanggenon A
Yoshio Hano, Ryuichi Kanzaki, Toshio Fukai, and Taro Nomura*
*Faculty of Pharmaceutical Sciences, Toho University, 2-2-1, Miyama, Funabashi, Chiba 274-8510, Japan
Abstract
The structure of sanggenon A, which has been isolated from the Chinese crude drug "Sang-Bai-Pi", was revised on the basis of two-dimentional NMR spectroscopic and chemical evidence. Sanggenon A is a unique 3-hydroxyflavanone derivative bearing an isoprenyl group at the C-2 position of the skeleton. The other flavanones having sanggenon A-type structure, including sanggenons M and C, also required the revision of the structure.
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■ Synthesis of N-Substituted 2,4-Diaminothiazoles and Their Salts
Ronald Flaig and Horst Hartmann*
*Fachbereich Chemie und Umweltingenieurwesen, Fachhochschule Merseburg, Geusaer Str., D-06217 Merseburg, Germany
Abstract
A series of N(2),N(4)-subsituted 2,4-diaminothiazoles (22) and their corresponding mineral acid salts (22·HX) and (22·2HX) have been prepared by the reaction of POCl3 with N-substituted S-(dialkylaminocarbonylmethylene)isothiouronium salts (20) available from corresponding substituted thioureas (18) and N,N-disubstituted chloroacetamides (19) or by the reaction of primary or secondary amines (25) in excess with N(2)-unsubstituted or N(2)-disubstituted 2-amino-4-thiazolinimine hydrochlorides (24) availabe by the reaction of corresponding N-substituted thioureas (18) with chloroacetonitirle (23).
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■ Reaction of Aryl Bromomethyl Ketone Phenylsulfonylhydrazones with Benzylideneaniline
Suketaka Ito,* Akikazu Kakehi, Kyoko Okada, Saori Goto, and Hiroshige Kawaguchi
*Depatment of Indusrial Chemistry, Faculty of Engineering, Shinshu University, 4-17-1 Wakasato, Nagano 380-8553, Japan
Abstract
6-Aryl-3,4-diphenyl-2-phenylsulfonyl-2,3,4,5-tetrahydro-1,2,4-triazines and 4-aryl-1-phenyl-1,2,3-triazoles were obtained in moderate yields by the reaction of aryl bromomethyl ketone phenylsulfonylhydrazones with benzylidnenaniline.
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■ A Novel Method of Preparation of 3-Acylimidazo[1,2-a]pyridines
Jean-Luc Moutou, Martine Schmitt, Valérie Collot, and Jean-Jacques Bourguignon*
*Laboratoire de Pharmacochimie Moleculaire, Faculte de Pharmacie, ULP, 74, route du Rhin 67401 ILLKIRCH Cedex, France
Abstract
A series of 2-substituted 3-acylimidazo[1,2-a]pyridines were synthesized in good to moderate yields from secondary amidino ketones and bromine in acetic acid. Cyclocondensation of the α-bromo-β-amidino ketones (6) led to the corresponding trans-dihydroimidazoles (13), which may yield spontaneously the stable 3-acylimidazo[1,2-a]pyridines (2) after dehydrogenation.
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■ (3aR*,6aS*)-5,5-Diphenyl-2,3,3a,4,6,6a-hexahydrosilolano[3,4-b]furan-2-one: A New Fused γ-Butyrolactone
Dominique Damour, Gilles Doerflinger, and Serge Mignani*
*Rhône-Poulenc Rorer S.A., Centre de Recherche de Vitry-Alfortville, 13 Quai Jules Guesde, BP 14, 94403, Vitry-sur-Seine Cedex, France
Abstract
The title fused γ-butyrolactone (1) was prepared in four steps, starting from 1,1-diphenyl-1-silacyclopent-3-ene.
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■ Coriacyclodienin and Coriacycloenin: Two New Annonaceous Acetogenins from Annona coriacea
Edna Lucia Meneses Da Silva, François Roblot, and André Cavé*
*Faculté de Pharmacie, Laboratoire de Pharmacognosie, URA 1843 CNRS (BIOCIS), 5 rue J.B. Clément 92296 Châtenay-Malabry Cedex, France
Abstract
Two new Annonaceous acetogenins, coriacyclodienin (1) and coriacycloenin (2), have been isolated from the roots of Annona coriacea Mart. (Annonaceae). 1 is the first mono-THF acetogenin which bears two double bonds in the aliphatic chain, which 2 has the same mono-THF ring and only one double bond. Both compounds (1) and (2) were oxidized and cyclized, in a one pot reaction, to give the mixtures of the four possible stereoisomer derivatives (3, 4, 5 and 6) of 1 and the two possible stereoisomer derivatives (7 and 8) of 2. The absolute stereochemistries of 1 and 2 were assigned using NMR analysis of their Mosher esters and enzymatic method.
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■ 2-[Arylamino(imino)]perhydropyrido-[1,2-d][1,3,4]oxadiazine and 2-[Aryl-amino(imino)]-perhydropyrrolo[1,2-d]-[1,3,4]oxadiazine: Heterocyclic Ring Systems Involving a Bridge-Head Nitrogen
Ari Rosling, Ferenc Fülöp, Reijo Sillanpää, and Jorma Mattinen*
*Department of Organic Chemistry, Åbo Akademi University, Biskopsgatan 8, FIN-20500 Åbo, Finland
Abstract
Hydrazino alcohols (1 - 4) were converted with phenyl or 4-chlorophenyl isothiocyanate into their thiourea derivatives (5a,b, 6a,b, 9a,b and 10a,b) which then were cyclized by treatment with methyl iodide and alkali to furnish 2-[arylamino(imino)]perhydropyrido[1,2-d][1,3,4]oxadiazines (7a,b) and perhydropyrrolo[1,2-d][1,3,4]oxadiazines (12a,b) and their 2-arylimino-3N-methyl derivatives (8a,b and 13b). The nmr spectra and X-ray crystallographic analysis indicated that the 1,3,4-oxadiazines adopt rigid cis- or trans-fused ring conformations, depending on the parent ring size and the 3N-substituent. It was found that in the unsubstituted 1,3,4-oxadiazines (7a,b and 12a,b) involving a potential tautomeric equilibrium. The amino form is most likely to predominate.
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■ Synthetic Route to α-Phosphono-γ-butyrolactones: Synthesis of γ-Substituted α-Methylene-γ-butyro-lactones
Chi-Wan Lee, Jun Mo Gil, and Dong Young Oh*
*Department of Chemistry, Korea Advanced Institute of Science and Technology, 373-1, Kusung-Dong, Yusung-Gu, Taejon, 305-701, Korea
Abstract
Treatment of lithiated homoallylic phosphonates wiht dimethyl carbamyl chloride gave 2-amidophosphonate derivatives. A solution of 2-amidophosphonate in DME-H2O (2:1 vol) reacted with 2 eq. iodine at room temperature to give α-phosphono-γ-iodoalkyl-γ-butyrolactones in good yield, although the products are mixture. Wadsworth-Emmons reaction of α-phosphono-γ-iodoalkyl-γ-butyrolactones with aldehydes gave α-(alkyl)methylene-γ-iodoalkyl-γ-butyrolactone derivatives.
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■ The Thermal Dimerization of Pyrano[3,2-c]coumarins
Giovanni Appendino, Giovanni Palmisano,* Silvia Tagliapietra, Gian Mario Nano, Luisella Calabi, and Lino Paleari
*Dipartimento di Scienza, Tecnologia del Farmaco, via P. Giuria 9, I-10125 Torino, Italy
Abstract
The thermal dimerization of the pyrano[3,2-c]coumarin (1) gave a mixture of four dimeric compounds, whose structure was established by extensive NMR studies.
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■ An Original Way for Synthesis of New Nitrobenzothiadiazole Derivatives
Patrice Vanelle,* Céline Tremblais Liegeois, Jacobine Meuche, José Maldonado, and Michel P. Crozet
*Laboratorie de Chimie Organique, Université d' Aix-Marseille 2, Faculté de Pharmacie, 27 Bd. Moulin, 13385 Marseille Cedex 05, France
Abstract
The C-alkylation reaction of 4-chloromethyl-7-nitro-2,1,3-benzothiadiazole with 2-nitropropane anion which is shown to proceed by an SRN1 mechanism is an original way for the synthesis of new 2,1,3-benzothiadiazoles.
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■ Model Study for the Construction of C Ring of Pimara Type Diterpenes
Takashi Fukumoto, Minoru Oguchi, Yoshinobu Kashibuchi, and Tadahiro Kato*
*Department of Chemistry, Faculty of Science, Science University of Tokyo, Kagurazaka 1-3, Shinjuku-ku, Tokyo 162-8601, Japan
Abstract
As the model experiment to explore the construction route of our synthetic intermediate (8), the epoxy alcohol (5) was prepared by Sharpless epoxidation including asymmetric introduction of the epoxide ring. The cyclization of 5 to the diol (6) proceeded in 40% yield by the action of Ti(OiPr)4 at room temperature. The diol (6) having more than 90% enantiomeric excess was obtained from the asymmetric epoxide (5).
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■ Pyrano- and Furocarbazole Alkaloids from the Root Bark of Clausena excavata
Tian-Shung Wu,* Shiow-Chyn Huang, and Pei-Lin Wu
*Department of Chemistry, Natioanl Cheng Kung University, Tainan, 70101, Taiwan, R.O.C.
Abstract
Two pyranocarbazole alkaloids, clausine-W (1) and clausine-T (2), as well as two furocarbazole alkaloids, furoclausine-A (3) and furoclausine-B (4), were isolated and identified from the acetone extract of the root bark of Clausena excavata. Their structures have been elucidated by spectroscopoic analyses.
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■ Furopyridines. Synthesis and Properties
Shunsaku Shiotani*
*Department of Chemistry, Faculty of Science, Toyama University, Gofuku 3190, Toyama 930, Japan
Abstract
This review describes the synthesis of the frameworks of furo[2,3-b]-, -[3,2-b]-, -[2,3-c]- and -[3,2-c] pyridine, and reactions of the furopyridines: such as bromination, nitration, H-D exchange and lithiation at the furan ring, chlorination, acetoxylation and cyanation of the N-oxides of furopyridines and 2,3-dihydrofuropyridines, and conversion of each substituent into other functional groups.