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. 41, No. 9, 1995
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■ The Syntheses of 1α-Fluoro-1β-methylcarbapenem Esters
Kenneth J. Wildonger, William J. Leanza, Ronald W. Ratcliffe, and James P. Springer
*Department of Medicinal Chemistry, Merck Research Laboratories, P.O.Box 2000, Rahway, NJ 07065, U.S.A.
Abstract
The synthesis of p-nitrobenzyl (1S,3R,5S,6S)-1-fluoro-1-methyl-2-oxo-6-[(1R)-1-[(tert-butyldimethylsilyl)oxyl]ethyl]carbapenam-3-carboxylate and allyl (1R,5S,6S)-6-[(1R)-1-[(allyloxycarbonyloxy)ethyl]-1-fluoro-1-methyl-2-phenylcarbapen-2-em-3-carboxylate is detailed. The difficulties encountered in further chemical elaboration of these analogs are reported.
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■ Formation of a Dimeric Complex of 14-Dicyanomethylene-5,8,21,24-tetraoxa-2,11,18,27-tetrathiatricyclo[26.4.1.112,17]tetratriaconta-12,15,17(34),28,30,32-hexaen-33-one with Mercury(II) Chloride
Nobuo Kato, Kanji Kubo, Akira Mori, and Hitoshi Takeshita
*Institute of Advanced Material Study, 86, Kyushu University, Kasuga-koen, Kasuga, Fukuoka 816, Japan
Abstract
14-Dicyanomethylene-5,8,21,24-tetraoxa-2,11,18,27-tetrathiatricyclo[26.4.1.112,17]tetratriaconta-12,15,17(34),28,30,32-hexaen-33-one, a thiocrown ether, having a large cavity for complexation, formed a 1:2-complex with HgCl2. The X-ray structural analysis revealed that two aromatic rings were almost planar and, of the eight heteroatoms of the ethereal ring, each set of the consecutive two oxygen atoms and one sulfur atom on the tropone ring coordinated to one Hg2+ ion, but two sulfur atoms on the heptafulvene part were free from the coordination. The interatomic distance of two Hg2+ was 4.248 Å.
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■ Simple Total Syntheses of Marine Alkaloids, Batzelline C, Isobatzelline C, Damirone A, and Makaluvamine A
Fumio Yamada, Shin Hamabuchi, Aya Shimizu, and Masanori Somei
*Faculty of Pharmaceutical Scicences, Kanazawa University, 13-1 Takara-machi, Kanazawa 920, Japan
Abstract
Batzelline C and isobatzelline C were synthesized in eight (or nine) steps from indole-3-carboxaldehyde. Syntheses of damirone A and makaluvamine A are also reported.
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■ Total Synthesis of Sanjoinine-G1
Byung Hoon Han, Yong Chul Kim, Man Ki Park, Jeong Hill Park, Hyun Jung Go, Hyun Ok Yang, Dae-Yeon Suh, and Young-Hwa Kang
*Natural Products Research Institute, Seoul National University, 28 Yunkeun-dong, Jongno-ku, Seoul 110-460, Republic of Korea
Abstract
Sanjoinine-G1 (1), a 14-membered cyclopeptide, was synthesized with stereoselective reactions. Started from D-serine, a cyclic precursor for various frangulanine type 14-membered cyclopeptide alkaloids was synthesized and the side chain acylation product was identical with the natural sanjoinine-G1 (17 steps, overall yield 1.36%).
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■ Synthesis of 5-Phosphonyl-2(1H)-pyridones from Primary β-Enaminophosphonate and Acetylenic Esters
Francisco Palacios, Jesús García, Ana Ma Ochoa de Retana, and Julen Oyarzabal
*Departamento de Química Orgánica, Facultad de Farmacia, Universidad del País Vasco, Apto. 450, 01080 Vitoria, Spain
Abstract
Primary β-enaminophosphonates (2) are obtained from metallated diethyl methylphosphonate and nitriles. Reaction of enamines (2) with ethyl propiolate and dimethyl acetylenedicarboxylate yields 1:1 adducts (7) and (8), respectively. Treatment of monoadducts (7) with sodium hydride leads to 5-phosphonyl-2(1H)-pyridones (1). Functionalized enamines (8) undergo thermal cyclocondensation to give pyridones (9).
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■ Inulavosin, a New Thymol Dimer with Piscicidal Activity from Inula nervosa
Takashi Yoshida, Kazuko Mori, and Guangxin He
*Faculty of Pharmaceutical Sciences, Okayama University, Tsushima, Okayama 700, Japan
Abstract
Upon the fractionation guided by piscicidal activity using the Medaka (Oryzias latipes), three piscicidal substances were isolated from the root of Inula nervosa, and were characterized as thymol and its derivatives based on the spectral analyses including 2D nmr techniques. A new piscicide, named inulavosin, was a thymol dimer with a new heterocyclic skeleton.
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■ A New Approach to Chiral 5,5-Disubstituted 2-Pyrrolidinones form (S)-Pyroglutamic Acid
Tatsuo Nagasaka and Tomoko Imai
*Tokyo University of Pharmacy and Life Science, School of Pharmacy, 1432-1 Horinouchi, Hachioji, Tokyo 192-03, Japan
Abstract
Two enantiomers of 5,5-disubstituted 2-pyrrolidinones with the certain configurations were synthesized, starting from (S)-pyroglutamic acid, via the bicyclic lactam, (2R,5S)-2-aryl-1-aza-3-oxabicyclo[3.3.0]oct-5-en-7-one (6).
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■ Asymmetric Synthesis with Chiral Hydrogenolysable Amines: A New Route to Enantiopure Cyclic β-Amino Alcohols
Olivier Lingibé, Bernadette Graffe, Marie-Claude Sacquet, and Gérard Lhommet
*Université P. et M. Curie, Laboratoire de Chimie des Hétérocycles, associé au CNRS, 4 Place Jussieu, F-75252 Paris Cedex 05, France
Abstract
Enantiopure prolinol and pipecolinol have been obtained via diastereoselective chemical reduction of chiral 2,3-dihydro-6H-1,4-oxazin-2-ones (5).
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■ Preparation of 2,4-Dialkylidene-1,3-dithietanes from Ynamines and Carbon Disulfide
Isao Shibuya, Midori Goto, Akihiro Oishi, Tohru Tsuchiya, Yoichi Taguchi, and Juzo Nakayama
*National Institute of Materials and Chemical Research, 1-1 Higashi, Tsukuba, Ibaraki 305, Japan
Abstract
Aminoacetylenes R2N-C ≡ C-R’ (1) afforded 2,4-dialkylidene-1,3-dithietanes (2) on compressing or heating with carbon disulfied. The structure of 2 was determined by X-ray crystal structure analysis. Thiocarbamoylthioketenes, 1:1 adducts of the ynamine and carbon disulfide were proposed as the probable intermediates leading to 2. The present results indicate that the reactivities of ynamines toward carbon disulfide are different from those of electron-deficient acetylenes.
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■ A Photochemical Approach to Spiranic 2,3-Indolines, Useful Intermediates in Pentacyclic Indole Alkaloid Synthesis
Malika Ibrahim-Ouali, Marie-Eve Sinibaldi, Yves Troin, Annie Cuer, Gérard Dauphin, and Jean-Claude Gramain
*URA 485 CNRS, Chimie des Substances Naturelles, Université Blaise Pascal, 63177 Aubière Cedex, France
Abstract
Spirolactones (4) and (5) were obtained by photocyclization of arylenaminolactones (8) and (9). The stereochemistry of the ring junction in tricyclic spiranic compounds was determined by NOE difference spectroscopy.
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■ A Simple Preparation of 3-Carbamoylfuro[2,3-b]quinoxalin-2-ones
Tadashi Okawara, Shigenori Matsumoto, Masashi Eto, Kazunobu Harano, and Mitsuru Furukawa
*Faculty of Pharmaceutical Sciences, Kumamoto University, Oe-hon-machi, 5-1, Kumamoto 862, Japan
Abstract
A preparation of 3-carbamoylfuroquinoxalin-2-ones (4a-g) was easily achieved by treatment of 3-methoxycarbonylmethylene-2-oxoquinoxalines (1a,b) and isocyanates (2a-d) with sodium hydride in dimethyl sulfoxide. The structure of 4c was confirmed by a single crystal X-ray structure determination.
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■ 6-Oxo-6a,12a-dehydro-α-toxicarol, a 6-Oxodehydrorotenone from the Roots of Derris oblonga Benth
Yun-Lian Lin and Yueh-Hsiung Kuo
*Department of Chemistry, National Taiwan University, Taipei, Taiwan, R.O.C.
Abstract
A 6-oxodehydrorotenone, 6-oxo-6a,12a-dehydro-α-toxicarol, together wih nineteen known compounds containing sugar, triterpenes, isoflavones, anthraquinones, rotenone, dehydrorotenones, 12a-hydroxyrotenones, coumestans, coumaronochromones and pterocarpen, were isolated from the roots of Derris oblonga, and characterized on the basis of spectral and chemical evidence.
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■ A Study of 2-Propenethials Obtained by Flash Vacuum Pyrolysis of 2-Ethenyl-1,3-dithiolane 1,1-Dioxides
Li-Fan Liao, Pen-Wen Tseng, Chin-Hsing Chou, Wen-Chih Chou, and Jim-Min Fang
*Department of Chemistry, National Taiwan University, Taipei 106, Taiwan, R.O.C.
Abstract
Synthesis of substituted 2-propenethials by the flash vaccum pyrolysis of appropriately substituted 2-ethenyl-1,3-dithiolane 1,1-dioxides has been investigated. Pyrolysis of 2-propenyl-1,3-dithiolane 1,1-dioxide (5a) gives thiophene, 2,5-dihydrothiophene, a [4+2] dimer (11) and a [4-+4] dimer (12) of 2-butenethial (4a). Pyrolysis of 2-(1-methylpropenyl)-1,3-dithiolane 1,1-dioxide (5b) gives 3-methylthiophene and a [4+4+4] trimer (14) of 2-methyl-2-butenethial (4b). Pyrolysis of 2-(2-phenylethenyl)-1,3-dithiolane 1,1-dioxide (5c) gives 2H-1-benzothiin (15) and a [4+2] dimer (16) of 3-phenyl-2-propenethial (4c). The dimer (11), 2-propenyl-4-methyl-4H-1,3-dithiin, can be considered as the meta-substituted cycloaddition product of 2-butenethial, whereas the dimer (16), 3-(2-phenylethenyl)-4-phenyl-3,4-dihydro-1,2-dithiin, can be considered as the ortho-substituted cycloaddition product of 2-phenyl-2-propenethial.
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■ Improved Synthesis of Esculetin
Yvette A. Jackson
*Department of Chemistry, University of the West Indies, Mona, Kingston 7, Jamaica, West Indies
Abstract
An improved synthesis of esculetin (6,7-dihydroxycoumarin) and 3-hydroxy-6,7-dimethoxycoumarin (4a) is described.
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■ Heck Annulation on 2-Position of Indoles or 1H-Pyrrolo[2,3-b]pyridine
Eric Desarbre and Jean-Yves Mérour
*Laboratoire de Chimie Bioorganique et Analytique, URA-CNRS n°499, Université d'Orléans, BP 6759, 45067 Orléans Cedex 2, France
Abstract
1-Substituted 3-formylindoles lead to annulated indolo[2,1-a]isoquinoline or pyrrolophenanthridine via palladium coupling. Under the same conditions 1-substituted 7-azaindoles afforded the 7-aza analogues.
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■ Synthesis of 1,3-Disubstituted 1,2,4-Triazolo[4,3-a]quinazolin-5-one Derivatives
Hyam A. Abdelhadi, Tayseer A. Abdallah, and Hamdi M. Hassaneen
*Department of Chemistry, Faculty of Science, University of Cairo, Giza, Egypt
Abstract
Treatment of hydrazonoyl halides 8 with 2-mercapto-4(3H)-quinazolinone (7) in refluxing chloroform in the presence of triethylamine afforded 1,3-disubstituted 1,2,4-triazolo[4,3-a]quinazolin-5-one derivatives.
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■ Stereoselective Synthesis of Optically Active Diethanolamines Utilizing Diastereoselective Reaction of 1,3-Oxazolidines with Grignard Reagents
Kimio Higashiyama, Katuyuki Nakagawa, and Hiroshi Takahashi
*Faculty of Pharmaceutical Science, Hoshi University, Ebara 2-4-41, Shinagawa-ku, Tokyo 142, Japan
Abstract
The highly diastereoselective addition of isopropoxydimethylmagnesium chloride to N-benzyl-1,3-oxazolidines derived from (R)-phenylglycinol, followed by oxidation of adducts with hydrogen peroxide in the presence of potassium fluoride, provided the 1-substituted (1R,1’R)-N-benzyl-1’-phenyl-2,2’-dihydroxydiethylamines (1a-d).
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■ Effective Strategy for the Synthesis of Pyrido[1',2':1,2]imidazo[5,4-c]isoquinoline System
Olivier Chavignon, Mohamed Raihane, Patricia Deplat, Jean Louis Chabard, Alain Gueiffier, Yves Blache, Gérard Dauphin, and Jean Claude Teulade
*Département d'Analyse Structurale et de Pharmacologie, Laboratoire de Chimie Organique, Faculté de Pharmacie, 28 Pl. H. Dunant, B.P. 38, 63001 Clermont-Ferrand CEDEX 1, France
Abstract
Annulation of 3-aceta(benza)mido-2-phenylimidazo[1,2-a]pyridines (2a,b) by phosphorus oxychloride results in the formation of pyridoimidazoisoquinolines (3a,b) as potent antileukemic structures. An alternative route for obtaining the isoquinoline framework was centered on the aza-Wittig reaction of iminophosphorane (4) with different isocyanates.
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■ Preparation of 15-Hydroxy-Δ13,14-milbemycin A4 and Its Transformation to 13-Alkylmilbemycins
Satoru Naito, Makio Kobayashi, and Akio Saito
*Medicinal Chemistry Research Laboratories, Sankyo Co., Ltd., 1-2-58 Hiromachi, Shinagawa-ku, Tokyo 140, Japan
Abstract
13-Alkylmilbemycins were synthesized regiospecifically by Claisen rearrangement of a 15-hydroxy-Δ13,14-milbemycin derivative, which was prepared selectively from a 14,15-epoxymilbemycin derivative by isomerization of the 14,15-epoxide moiety induced by ethylaluminum bis(2,6-diphenylphenoxide).
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■ Synthesis of Perhydro-1,3,4-thiadiazin-5-ones and 3-Arylaminothiazolidin-4-ones by the Regioselective Cyclocondensation of 2-Sulfanylalkanoic Acids or Their Silyl Esters with Methyl and Aryl Hydrazones
Yoo Tanabe, Masaki Nagaosa, and Yoshinori Nishii
*School of Science, Kwansei Gakuin University, 1-1-155 Uegahara, Nishinomiya, Hyogo 662, Japan
Abstract
Perhydro-1,3,4-thiadiazin-5-ones and 3-arylaminothiazolidin-4-ones were prepared by the highly regioselective cyclocondensation of 2-sulfanylalkanoic acids with methyl- and arylhydrazones, respectively. A similar reaction using trimethylsilyl 2-sulfanylalkanoates in the place of the acids proceeded under milder conditions with tetrabutylammonium fluoride catalyst.
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■ A Chemistry of Bisbenzylisoquinoline Alkaloid: Isomerization of Berbamine to Penduline in Methanol by Radical Reaction
Noriaki Kashiwaba, Shigeo Morooka, Michiko Kimura, Minoru Ono, Yoshie Murakoshi, Jun Toda, and Takehiro Sano
*Research Laboratories, Kaken Shoyaku Co., Ltd., 3-37-10, Shimorenjaku, Mitaka-shi, Tokyo 181, Japan
Abstract
Berbamine (1), a bisbenzylisoquinoline alkaloid, when treated with methanol, was isomerized to penduline (2), the C-1 epimer of 1. This isomerization was proved to proceed via a radical reaction by a free radical generated from methanol and molecular oxygen.
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■ Two Novel Sarpagine-Type Indole Alkaloids from the Leaves of Hunteria zeylanica in Thailand
Sanan Subhadhirasakul, Hiromitsu Takayama, Yuhko Miyabe, Mariko Kitajima, Dhavadee Ponglux, Shin-ichiro Sakai, and Norio Aimi
*Faculty of Pharmaceutical Sciences, Chiba University, 1-33 Yayoi-cho, Chiba 263, Japan
Abstract
The chemical investigation of the leaves of Hunteria zeylanica (Retz) Gardn. ex Thw., collected in Thailand, resulted in the isolation of two new sarpagine-type indole alkaloids, Nb-methyl-3α-amino-seco-voacarpine and hunteriatryptamine, along with twelve known bases.
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■ Tautomerism and Isomerism of Heterocycles [2]
Yoshihisa Kurasawa, Atsushi Takada, and Ho Sik Kim
*School of Pharmaceutical Sciences, Kitasato University, Shirokane, Minato-ku, Tokyo 108, Japan
Abstract
This review describes tha tautomerism of various heterocyclic compounds between the enamine and methylene imine forms, between the enamine and enol imine forms, and between the azo and hydrazone forms together with the isomerism of some heterocycles.
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■ Photoinduced Molecular Rearrangements of O-N Bond-containing Five-membered Heterocycles. An Assay for 1,2,4- and 1,2,5-Oxadiazoles
Nicolò Vivona and Silvestre Buscemi
*Dipartimento di Chimica Organica, Università di Palermo, Via Archirafi 20, 90123 Palermo, Italy
Abstract
The photochemical behavior of 1,2,4- and 1,2,5-oxadiazoles is reviewed. Photoinduced molecular rearrangements of these five-membered rings are emphasized.