HETEROCYCLES
An International Journal for Reviews and Communications in Heterocyclic ChemistryWeb Edition ISSN: 1881-0942
Published online by The Japan Institute of Heterocyclic Chemistry
Special Issue
Leo A. Paquette's Special Issues, Vol. 62, No. 1, 2004
Published online: 17th November, 2003
■ Acid-catalyzed Cyclization Reactions of 2,2’-Bis(diarylhydroxymethyl)biphenyls to 5,5,7,7-Tetraaryl-5,7-dihydrodibenzo[c,e]oxepins in the Solid State
Shinya Hirano, Shinji Toyota, and Fumio Toda*
*Department of Chemistry, Faculty of Science, Okayama University of Science, 1-1 Ridai-cho, Okayama 700-0005, Japan
Abstract
Heating of 2:1 inclusion crystals of 2,2’-bis(hydroxydiphenylmethyl)biphenyl and formic acid in the solid state gave 5,5,7,7-tetraphenyl-5,7-dihydrodibenzo[c,e]oxepin in 89% yield. When mixtures of 2,2’-bis([bis(p-methoxyphenyl)hydroxymethyl]biphenyl and p-toluenesulfonic acid in 2:1 and 1:0.1 molar ratios were kept at room temperature for 80 min and 12 h, respectively, 5,5,7,7-tetra(p-methoxyphenyl)-5,7-dihydrobenzo[c,e]oxepin was obtained in quantitative yields. These are the first examples of an acid-catalyzed reaction in the solid state.
Published online: 18th November, 2003
■ Reactions of 2-, 3-, and 4-Quinolinols with Cyclohexane and Benzene in Superacids
Konstantin Yu. Koltunov, G. K. Surya Prakash,* Golam Rasul, and George A. Olah*
*Loker Hydrocarbon Research Institute and Department of Chemistry, University of Southern California, Los Angeles, California 90089-1661, U.S.A.
Abstract
Isomeric 2-, 3- and 4-quinolinols (11-13) underwent selective ionic hydrogenation with cyclohexane in CF3SO3H-SbF5 system to give 5,6,7,8-tetrahydro-2(1H)-quinolinone, 5,6,7,8-tetrahydro-3-quinolinol and 5,6,7,8-tetrahydro-4(1H)-quinolinone (28-30), respectively. When reaction was carried out in the presence of excess of aluminum chloride, 11 gave 3,4-dihydro-2(1H)-quinolinone (31), whereas 13 gave the product (30). Compounds (11) and (13) condense with benzene in the presence of aluminum halides producing phenyl substituted derivatives of 28, 31 and 30 (products 32-34), respectively. The mechanism of these and related reactions involving superelectrophilic dicationic intermediates is discussed.
Published online: 14th October, 2003
■ [2π+2σ] Type Cycloaddition Reactions of Naphtho[b]cyclopropene with Trithiocarbonyl Compounds to Form 1,3-Dihydronaphtho[2,3-c]thiophene Derivatives
Katsuhiro Saito,* Yasuhiro Ohzone, Yoji Kondo, Katsuhiko Ono, and Masakazu Ohkita
*Department of Applied Chemistry, Faculty of Engineering, Nagoya Institute of Technology, Gokiso-cho, Showa-ku, Nagoya 466-8555, Japan
Abstract
Reactions of naphtho[b]cyclopropene with trithiocarbonyl derivatives in chloroform afforded 1,3-dihydrobenzo[2,3-c]thiophene derivatives in moderate yields through a [2π + 2σ] type cycloaddition process. The similar reaction with a dithiocarbonate compound gave a recovery of the starting material. A reaction with thiotropone resulted in a [8π + 2σ] type adduct in 5% yield. Solvent effects on the product yields revealed that the reactions proceeded via ionic intermediates.
Published online: 28th April, 2003
■ A Novel, Expedient Synthesis of Thiazolo[4,5-c]- and -[5,4-b]carbazoles
Manas Chakrabarty,* Nandita Ghosh, and Yoshihiro Harigaya
*Department of Chemistry, Bose Institute, 93/1, A. P. C. Road, Kolkata-700009, India
Abstract
A new synthesis of thiazolo[4,5-c]- and -[5,4-b]carbazoles (6a-e, 7a, 8b-e) was accomplished from 3-aminocarbazoles (3a-e) by separate condensations with methyl and phenyl isothiocyanates, followed by oxidative cyclization of the resulting thioureidocarbazoles (4a-e, 5a).
Published online: 28th April, 2003
■ A Formal Total Synthesis of (-)-Limaspermine
Yu-ichi Fukuda, Mitsuru Shindo, and Kozo Shishido*
*Institute for Medicinal Resources, University of Tokushima, 1-78 Sho-machi, Tokushima 770-8505, Japan
Abstract
An enantiocontrolled formal total synthesis of an aspidosperma indole alkaloid (-)-limaspermine has been accomplished using a diastereoselective ring-closing metathesis for formation of the quaternary stereogenic center.
Published online: 6th October, 2003
■ The Fungicidal Benzothiazole Methoxyacrylates: Synthesis, Conformational Analysis and Fungicidal Activity
Choon Sup Ra,* Bon Young Jung, and Gyoosoon Park*
*Department of Chemistry, Yeungnam University, Kyongsan 712-749, Korea
Abstract
Synthesis of a series of novel benzothiazole methoxyacrylate compounds (3-4) based on the antifungal natural product, Strobilurin A is described. Fungicidal activities of 3-4 against six representative fungal diseases and their comparative conformational analyses vs Strobilurin A are accounted.
Published online: 14th October, 2003
■ Concise Synthesis of 11H-Indolizino[1,2-b]quinolin-9-one by an Aryl-Aryl Coupling Reaction Using Pd Reagent
Takashi Harayama,* Yosiaki Morikami, Akihiro Hori, Hiromi Nishioka, Hitoshi Abe, and Yasuo Takeuchi
*Faculty of Pharmaceutical Sciences, Okayama University, 1-1-1 Tsushima-naka, Okayama 700-8530, Japan
Abstract
The biaryl coupling reaction of 1-[(2-bromoquinoline-3-yl)methyl]-2(1H)-pyridinone using a catalytic amount of palladium acetate, tricyclohexylphosphine, and potassium acetate in DMF proceeded smoothly to give 11H-indolizino[1,2-b]quinolin-9-one in excellent yield.
Published online: 27th October, 2003
■ An Efficient Preparative Route to 7-Ethyl-1H-furo[2,3-g]indazole
Itsuro Shimada,* Kyoichi Maeno, Tetsuya Kimizuka, Seiki Goto, Takumi Takahashi, Atsushi Nakamura, Akio Miyafuji, Shin-ichi Tsukamoto, and Shuichi Sakamoto
*Institute for Drug Discovery Research, Yamanouchi Pharmaceutical Co., Ltd., 21, Miyukigaoka, Ibaraki 305-8585, Japan
Abstract
A new and efficient route to 7-ethyl-1H-furo[2,3-g]indazole (2) has been developed. Treatment of 4,5-dihydro-7-(1-hydroxyethyl)indazole (12) with hydrochloric acid in ethanol resulted in a concomitant dehydration and aromatization to afford the title compound in good yield.
Published online: 27th October, 2003
■ Regioselective Synthesis of 6- and 7-Substituted Thiazolo[3,2-a]benzimidazole Derivatives Using Crystallization Induced Regioisomerization
Satoshi Hayashibe,* Takashi Kamikubo, Shin-ichi Tsukamoto, and Shuichi Sakamoto
*Institute for Drug Discovery Research, Yamanouchi Pharmaceutical Co., Ltd., 21, Miyukigaoka, Ibaraki 305, Japan
Abstract
An efficient regioselective synthesis of 2-methoxycarbonylthiazolo[3,2-a]benzimidazole-6-carboxylic acid (2) and 2-methoxycarbonylthiazolo[3,2-a]benzimidazole-7-carboxylic acid (3) have been developed.
Published online: 14th November, 2003
■ Synthesis and Properties of Azaperylenedicarboximide Derivative
Yukinori Nagao,* Eri Shimokoshi, and Kozo Kozawa
*Department of Industrial Chemistry, Faculty of Science and Technology, Science University of Tokyo, 2641 Yamazaki, Noda, Chiba 278-8510, Japan
Abstract
Azaperylenedicarboximide derivative was prepared by coupling of N-pentyl-4-tributylstannylnaphthalene-1,8-dicarboximide with 4-bromo-1,8-dimethylisoquinoline in the presence of Pd(PPh3)4 and following ring closure reaction by using t-C4H9OK/DBN as base. Spectral properties of absorption and fluorescence in solution of the azaperylene derivative were investigated.
Published online: 27th October, 2003
■ Cyclofunctionalization of Unsaturated Alcohols, Phenols, Acids, and Sulfonamides with 1-Benzenesulfinyl Piperidine and Trifluoromethanesulfonic Anhydride
David Crich,* Bhushan Surve, and Mousumi Sannigrahi
*Department of Chemistry, University of Illinois at Chicago, 845 West Taylor St., Chicago, IL 60607-7061, U.S.A.
Abstract
The combination of a benzenesulfinamide, trifluoromethanesulfonic anhydride, and Hünig’s base brings about the cyclofunctionalization of unsaturated alcohols, phenols, acids, and sulfonamides to give the corresponding α-phenylsulfanylmethyl cyclic ethers, lactones and sulfonamides, respectively. In an unanticipated twist the products are isolated at the sulfur (II) oxidation state denoting an overall reduction in the oxidation state of the sulfur based electrophile in the course of the reaction.
Published online: 14th November, 2003
■ Spiro Bis(isoxazole) as a New Chiral Ligand
Kazuhiko Wakita, Midori A. Arai, Takahiro Kato, Toshio Shinohara, and Hiroaki Sasai*
*The Institute of Scientific and Industrial Research, Osaka University, 8-1, Mihogaoka, Ibaraki, Osaka 567-0047, Japan
Abstract
A novel bis(isoxazole) ligand, (M*)-4,4’,5,5’,6,6’,7,7’-octahydro- 7,7’-spirobi[benzo[c]isoxazole] (5) bearing a spiro chirality was designed and synthesized. Characterization of the ligand and its application to the enantioselective tandem cyclizaton of alkenyl alcohol via oxy-palladation are described.
Published online: 14th November, 2003
■ New Access to Chiral Cyclic ω-Oxygenated β-Enamino Esters by Intramolecular Aminocyclisation Reactions
Olivier David, Corinne Vanucci-Bacqué, Marie-Claude Fargeau-Bellassoued, and Gérard Lhommet*
*Laboratoire de Chimie des Hétérocycles UMR 7611, Université P. et M. Curie, case courrier 43, 4 Place Jussieu, F-75252 Paris Cedex 05, France
Abstract
The preparation of chiral 4-methoxycarbonylmethylideneoxazolidines and oxazolidinone from (S)-1-phenylethylamine and hydroxy alkynoates is described. The extension of this strategy to 6- and 7-membered heterocyclic homologues is also reported.
Published online: 14th November, 2003
■ Reductive Methylation/Phosphorylation of 3,4-Diazacyclopentadienone N-Oxides with Trimethyl Phosphite
Jeremiah P. Freeman* and Marc E. Guay
*Department of Chemistry and Biochemistry, University of Notre Dame, 251 Nieuwland Science Hall, Notre Dame, IN 46556, U.S.A.
Abstract
Treatment of 2,5-diphenyl-3,4-diazacyclopentadienone 3-oxide and 3,4-dioxide with trimethyl phosphite results in N-deoxygenation and methylation and O-phosphorylation to produce dimethyl (1-methyl-3,5-diphenyl-4-pyrazolyl) phosphate.
Published online: 14th November, 2003
■ A Direct Approach to the Synthesis of 5-Aryl-4-chloropyridazinone: From Microwave Assisted Catalyst Screen to Room Temperature Regio- and Chemoselective Suzuki Arylation
Yong Gong and Wei He*
*Drug Discovery, Johnson & Johnson Pharmaceutical Research & Development, L. L. C., P. O. Box 776, Welsh and McKean Rds., Spring House, PA 19477-0776, U.S.A.
Abstract
Suzuki coupling of 4,5-dichloropyridazinone with phenylboronic acid yielded the desired 4-chloro-5-phenylpyridazinone along with 4-aryl and 4,5-diaryl derivatives. An extensive microwave-assisted screen led to the identification of Pd(PEt3)2Cl2 as an ideal catalyst with superior rate and selectivity. Further optimizations provided an effective, regioselective and chemoselective arylation method at room temperature.
Published online: 18th November, 2003
■ Asymmetric Synthesis of Panaxydol and Its Stereoisomers
Hsi-Jung Yu, Chang-Ming Sun, Chien-Chih Chen, Tsao-Chin Wu, Chia-Ling Wei, and Chien-Chang Shen*
*National Research Institute of Chinese Medicine, 155-1, Sec. 2, Li-Nung Street, Taipei 112, Taiwan, R.O.C.
Abstract
A facile synthesis of four possible stereoisomers of panaxydol was described. The configurations of C-3 and C-9, C-10 positions were established by enantioselective reduction and Sharpless asymmetric dihydroxylation, respectively.
Published online: 18th November, 2003
■ Syntheses of Oxazolidinone, Imidazolidinone and Thiazolidinone Derivatives Using a Polymer-supported Diphenylphosphoryl Azide
Yuhua Lu and Richard T. Taylor*
*Department of Chemistry, Miami University, Oxford, Ohio 45056, U.S.A.
Abstract
By using a polymer-supported diphenylphosphoryl azide (PS-DPPA), oxazolidinone, imidazolidinone and thiazolidinone derivatives were successfully prepared from carboxylic acids bearing different reactive functional groups in the β position , such as alcohols, thiols, primary or secondary amines. The desired compounds were obtained in good yields via Curtius rearrangement and subsequent intramolecular cyclization.
Published online: 28th April, 2003
■ Azabicyclo[2.1.1]hexanes. A Review
Grant R. Krow* and Kevin C. Cannon
*Department of Chemistry, Temple University, Philadelphia, PA 19122, U.S.A.
Abstract
The synthesis and reactions of 1-, 2-, and 5-azabicyclo[2.1.1]hexanes are reviewed.