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. 68, No. 11, 2006
Published online: 8th September, 2006
■ Novel Formation of 1,2-Dithiolane-3-thione from β-Dithiolactone
Toshiyuki Shigetomi, Akiko Nojima, Kosei Shioji, Kentaro Okuma,* and Yoshinobu Yokomori
*Department of Chemistry, Faculty of Science, Fukuoka University, Jonan-ku, Fukuoka 814-0180, Japan
Abstract
The sulfurization of β-dithiolactone gave 1,2-dithiolane-3-thione via an ionic intermediate. The reaction of 1,2-dithiolane-3-thione with acetylenedicarboxylate esters gave the corresponding spirocyclic 1,3-dithioles in good yields, whereas the reaction of 5-methyl-1,2-dithiole-3-thione with DMAD afforded a 1:2 cycloadduct in 78% yield.
Published online: 22nd September, 2006
■ Synthesis of 4-Arylpyrazoles via PdCl2(dppf)-Catalyzed Cross Coupling Reaction with Grignard Reagents
Hayato Ichikawa,* Yuuki Ohno, Yoshihide Usami, and Masao Arimoto
*Osaka University of Pharmaceutical Sciences, Nasahara Takatsuki, Osaka 569-1141, Japan
Abstract
4-Aryl-1-tritylpyrazoles were prepared from the cross coupling reaction of aryl Grignard reagents with 4-bromo-1-tritylpyrazoles in the presence of 0.2 mol% PdCl2(dppf) as catalyst. To deprotect the trityl group, 4-phenyl-1-tritylpyrazole was reacted with TFA to produce 4-arylpyrazole in quantitative yield.
Published online: 3rd October, 2006
■ Microwave-Assisted Cycloaddition Reaction of Azides to N-Substituted 2-Azabicyclo[2.2.1]hept-5-en-3-ones
Minoru Ishikura,* Miyako Hasunuma, Koji Yamada, and Reiko Yanada
*Faculty of Pharmaceutical Sciences, Health Sciences University of Hokkaido, Ishikari-Tobetsu, Hokkaido 061-0293, Japan
Abstract
The reaction of N-substituted 2-azabicyclo[2.2.1]hept-5-en-3-ones (ABH) (1) with azides (2,4) could be effected under microwave conditions, producing aziridine-fused ABH (3) and triazolines (5,6) in good yields.
Published online: 3rd October, 2006
■ Efficient Microwave Assisted Syntheses of Unsubstituted Cyclic Imides
Yousef M. Hijji* and Ellis Benjamin
*Department of Chemistry, Morgan State University, Baltimore, MD 21251.USA
Abstract
A number of cyclic imides were synthesized from cyclic anhydrides using ammonium chloride (NH4Cl), and 4-N,N-dimethylaminopyridine (DMAP) or with ammonium acetate (NH4OAc) under microwave irradiation in both a mono-mode and a conventional microwave. Several substituted succinic anhydrides used as reactants were synthesized efficiently by Diels-Alder reactions of maleic anhydride with 1,3-cyclohexadienes in 63-82% for the mono-mode and 72-92% in the conventional microwave ovens. Cyclic imides were synthesized with yields from 50 - 98%.
Published online: 22nd September, 2006
■ Synthesis of Novel 1,3,4-Oxadiazin-5(6H)-ones and 2-Hydroxymethyl-1,3,4-oxadiazoles
Agnieszka Kudelko* and Wojciech Zielinski
*Department of Organic Technology and Petrochemistry, Silesian University of
Technology, Ul. Krzywoustego 4, PL-44101 Gliwice, Poland
Abstract
Reactions of α-hydroxyacid hydrazides (benzilic, R- and S-mandelic) and triethyl orthoesters (orthoformate, orthoacetate, orthopropionate, orthobenzoate) in glacial acetic acid resulted in two groups of heterocyclic compounds, derivatives of 6-phenyl-1,3,4-oxadiazin-5-(6H)-one and 2 hydroxymethyl-1,3,4-oxadiazole. Their structures were confirmed by typical spectroscopic methods and X-Ray analysis. Spectral characteristic of the compounds and attempts to elucidate the mechanism are discussed.
Published online: 5th September, 2006
■ Synthesis, Crystal Structure Determination and Antiproliferative Evaluation of Novel Benzazoyl Benzamides
Kristina Starcevic, Irena Caleta, Dominik Cincic, Branko Kaitner, Marijeta Kralj, Katja Ester, and Grace Karminski-Zamola
*Department of Organic Chemistry, Faculty of Chemical Engineering and Technology, Marulicev trg 20, HR-10000 Zagreb, Croatia
Abstract
A series of benzazoyl-benzamides containing different substituents (7-17) were synthesized by condensation of 2-aminobenzazole derivatives (3a-6) with p-substituted benzoyl chlorides. All compounds were characterized by IR, 1H and 13C NMR, MS and elemental analysis. Crystal structure was determined for the compound (9). Some of the new synthesized compounds (7-17) were screened for antitumor activities. Based on presented in vitro screening results we may conclude that compounds (10, 15a, 15b and 16) showed accentuated cell growth inhibitory activity.
Published online: 1st September, 2006
■ Synthesis of Vinca Alkaloids and Related Compounds. Part 106. An Efficient Convergent Synthetic Pathway to Build Up the Ibophyllidine Skeleton II. Total Synthesis of (±)-Deethylibophyllidine and (±)-14-Epi-deethylibophyllidine
Flórián Tóth, György Kalaus,* István Greiner, Mária Kajtár-Peredy, Ágnes Gömöry, László Hazai, and Csaba Szántay*
*Department for Organic Chemistry, Research Group for Alkaloid Chemistry of the Hungarian Academy of Sciences, Budapest University of Technology and Economics, Gellért tér 4, H-1521 Budapest, Hungary
Abstract
Starting from 2,3-dihydrofuran (7) we prepared aldehyde (5) which, in a [4+2] cycloaddition reaction with the tryptamine derivative (4) gave, as a final step, compound (10) having a D-seco-aspidospermane skeleton. We synthesized (±)-14-epi-deethylibophyllidine (3) via the mesylate (12) of alcohol (11) which had been obtained from 10, whereas the cyclization of the benzoate ester (15) resulted in (±)-deethylibophyllidine (2). We have managed to build up (±)-2 via the tetracyclic intermediates (16) and (20).
Published online: 22nd September, 2006
■ Synthesis of New 1,2-Diphenyl-4,5-dihydro-3H-3-benzazepines
Chiaki Kaito, Kumiko Sakamoto, Mitsushi Sakamoto, Aiko Yamauchi, and Masaru Kihara*
*Faculty of Pharmaceutical Sciences, The University of Tokushima, 1-78, Sho- machi, Tokushima 770-8505, Japan
Abstract
1,2-Diphenyl-4,5-dihydro-3H-3-benzazepine derivatives (2a-d) were synthesized via cyclization reaction of N-[2-(2-iodophenyl)ethyl]-α- phenylphenacylamines (5a-c) and (5e) with n-C4H9Li, followed by dehydration of the cyclization products, 1,2-diphenyl-1-hydroxy-3-methyl-2,3,4,5-tetrahydro- 1H-3-benzazepines (4a-d) with trifluoromethanesulfonic acid.
Published online: 22nd September, 2006
■ L-Proline-Catalyzed Asymmetric Aldol Condensation of N-Substituted Isatins with Acetone
Gang Chen, Ye Wang, Hongping He, Suo Gao, Xiaosheng Yang, and Xiaojiang Hao*
*State Key Laboratory of Phytochemistry and Plant Resources in West China, Kunming Institute of Botany, Chinese Academy of Sciences, Kunming 650204, PR China
Abstract
L-proline-catalyzed asymmetric aldol condensation of several isatin derivatives with acetone is reported. The desired products were obtained in highly yield with the ee among 30-79%. The substitutes of N can deeply effect the ee value of products, and a novel mechanism is also described.
Published online: 12th September, 2006
■ Medicinal Foodstuffs. XXXII. Novel Sesquiterpene Glycoside Sulfate, Fukinoside A, with Antiallergic Activity from Japanese Butterbur (Petasites japonicus)
Masayuki Yoshikawa,* Toshio Morikawa, Junji Tanaka, and Hiroshi Shimoda
*Kyoto Pharmaceutical University, Misasagi, Yamashina-ku, Kyoto 607-8412, Japan
Abstract
Novel sesquiterpene glycoside sulfate, fukinoside A, was isolated as the potassium salt from the aerial parts of Petasites japonicus. The absolute sterostructure of fukinoside A was elucidated on the basis of chemical and physicochemical evidence. In addition, fukinoside A was found to inhibit release of β-hexosaminidase, as a marker of antigen-induced degranulation, in RBL-2H3 cells.
Published online: 22nd September, 2006
■ N,N,N’,N’-Tetrabromobenzene-1,3-disolfonamide (TBBDS) as an Efficient Promoter for One-Pot Conversion of N-Arylglycines to Sydnones in the Presence of NaNO2/Ac2O under Neutral Conditions
Davood Azarifar,* Hassan Ghasemnejad-Bosra, Ramin Ghorbani-Vaghei, and Mahmood Tajbaksh
*Department of Chemistry, School of Science, Bu-Ali Sina University, Postal Code 65174, Hamadan, Iran
Abstract
N,N,N’,N’-Tetrabromobenzene-1,3-disolfonamide (TBBDS)-promoted one-pot conversion of various N-arylglycines to sydnones using a combination of NaNO2 and Ac2O has been achieved efficiently through N-nitrosation followed by cyclization in high yields (85-95%) under mild and neutral conditions.
Published online: 22nd September, 2006
■ Regioselective Reaction of 2-Indolylcyanocuprates with Electrophiles
Minoru Ishikura,* Reina Uemura, Koji Yamada, and Reiko Yanada
*Faculty of Pharmaceutical Sciences, Health Sciences University of Hokkaido, Ishikari-Tobetsu, Hokkaido 061-0293, Japan
Abstract
The reaction of 2-indolylcyanocuprate with electrophiles was found to give rise to 2- and 3-substituted indoles in regioselective manner.
Published online: 6th October, 2006
■ Nankakurine B, a New Alkaloid from Lycopodium hamiltonii and Revised Stereostructure of Nankakurine A
Yusuke Hirasawa, Jun’ichi Kobayashi, Yutaro Obara, Norimichi Nakahata, Nobuo Kawahara, Yukihiro Goda, and Hiroshi Morita*
*Faculty of Pharmaceutical Sciences, Hoshi University, Shinagawa-ku, Tokyo 142-8501, Japan
Abstract
A new Lycopodium alklaoid, nankakurine B (2), has been isolated from the club moss Lycopodium hamiltonii together with nankakurine A (1). Stereochemistry of 2 was elucidated by combination of NOESY correlations and chemical transformation. Stereostructure of 1 was revised to be the same as that of 2. Nankakurine A (1) induced secretion of neurotrophic factors from human astrocytoma cells.
Published online: 29th September, 2006
■ Synthesis of Pipecolic Acid and Baikiain
Meng-Yang Chang,* Yung-Hua Kung, and Tsun-Cheng Wu
*Department of Applied Chemistry, National University of Kaohsiung, Kaohsiung 811, Taiwan, R.O.C.
Abstract
A straightforward synthesis of pipecolic acid and baikiain was achieved from trans-(2S,4R)-4-hydroxyproline via the key steps of regioselective Baeyer-Villiger reaction and ring-closing metathesis.
Published online: 8th September, 2006
■ Establishment of an Efficient Synthetic Route to 3,4:3’,4’-Bis(3,6,9-trioxaundecane-1,11-dioxy)benzil
Masaru Kimura,* Kun Shi, Koji Hashimoto, and Zhi Zhi Hu
*Department of Chemistry, Faculty of Science, Okayama University, Tsushima- Naka 3-1-1, Okayama 700-8530, Japan.
Abstract
3,4:3’,4’-Bis(3,6,9-trioxaundecane-1,11-dioxy)benzil (1) [bis(crown ether)benzil] was prepared by three different routes in which the third route C, including the method of Sonogashira-coupling, was the most efficient method with the overall yield of 50%. Further, the method of synthesizing the novel compound 3,4:3’,4’-bis[3,4-(3,6,9-trioxaundecane-1,11-dioxy)]benzoin (6) [bis(crown ether)benzoin], which has not yet been prepared appropriately, was also provided.
Published online: 12th September, 2006
■ Synthesis of 2-Aminomethylpyridine Derivatives of Phosphazenes
Saliha Begeç* and Sümeyya Alatas
*Inönü University, Faculty of Science and Arts, Chemistry Department, 44280 Malatya, Turkey
Abstract
Novel cyclophosphazenes (5-8) with pyridine side groups have been synthesized by the reactions of hexachlorocyclotriphosphazatriene, N3P3Cl6 (1), with 2-amino-3-methylpyridine (2), 2-amino-4-methylpyridine (3) and 2-amino-5-methylpyridine (4). Di- and monosubstituted products (5, 6) were obtained from the reaction of 1 with 2 and 3, respectively. Both di- and monosubstituted products (7, 8) were obtained from 2-amino-5-methylpyridine with 1. The structures of the compounds (5-8) were defined by IR, 1H, 13C and 31P NMR spectroscopy and elemental analyses.
Published online: 12th September, 2006
■ Synthesis and Antiviral and Antitumor Activities of 2H-[1,2,3]Triazolo[4,5-d]pyrimidines and 1H-, 2H-, and 3H-[1,2,3]Triazolo[4,5-d]pyrimidin-5(4H)-one-7(6H)-thiones
Rafiqul Islam and Tomohisa Nagamatsu*
*Department of Drug Discovery and Development, Division of Pharmaceutical Sciences, Graduate School of Medicine, Dentistry and Pharmaceutical Sciences, Okayama University, Tsushima, Okayama 700-8530, Japan
Abstract
This paper describes a facile synthesis of 2-aryl-2H-[1,2,3]triazolo- [4,5-d]pyrimidine-5,7(4H,6H)-diones (3a-o) and 7-amino-2-aryl-5-phenyl-2H- [1,2,3]triazolo[4,5-d]pyrimidines (6a-e) prepared by oxidative cyclization of 6- amino-5-arylazopyrimidine-2,4(1H,3H)-diones (2a-o) and 4,6-diamino-5- arylazo-2-phenylpyrimidines (5a-e) with CuSO4, respectively, and a reliable thionation of [1,2,3]triazolo[4,5-d]pyrimidine-5,7(4H,6H)-diones (3a,e,f, 7a,b and 9) accomplished by the reaction with phosphorous pentasulfide or Lawesson’s reagent as well as evaluation of their antiviral and antitumor activities in vitro.
Published online: 22nd September, 2006
■ Quaternary Benzo[c]phenanthridines Sanguinarine and Chelerythrine: a Review of Investigations from Chemical and Biological Studies
Zdenek Dvorák, Vlastimil Kubán, Borivoj Klejdus, Jan Hlavác, Jaroslav Vicar, Jitka Ulrichová, and Vilím Simánek*
*Department of Medical Chemistry and Biochemistry, Faculty of Medicine, Palacky University Olomouc, Hnevotinska 3, 77515 Olomouc, Czech Republic
Abstract
Sanguinarine and chelerythrine are intensively studied biologically active alkaloids for their potentially useful medicinal properties, such as antimicrobial, antiinflammatory, and antitumoral activities. This article aims to review critically recent literature published on the chemical behavior, synthesis, analytical methods and biotransformation of both alkaloids.