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
Masatomo Hamana's Special Issues, Vol. 33, No. 2, 1992
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■ Transition State Geometry in the Thermal Generation of Aryl- and Acylnitrenium Ions
Rudolph A. Abramovitch,* Qing Shi, and Santiago Olivella
*Department of Chemistry, Clemson University, Clemson, SC 29634-1905, U.S.A.
Abstract
Molecular mechanics and semiempirical AM1 calculations indicate that N -acyl- and N -alkylarylnitrenium ions generated by heterolysis of appropriate precursors are π-cations formed by the leaving group following a trajectory which moves it progressively out of the plane of the aromatic nucleus so that the transition state has appreciable π-cation character.
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■ Synthesis of Chiral Lactones and Triols from α-Acetyl-γ-butyrolactones by Use of Bakes's YEast
Mitsuhiro Takeshita,* Hiroko Yanagihara, and Sachiko Yoshida
*Tohoku Pharmaceutical University, 4-4-1 Komatsushima, Aoba-ku, Sendai 981-8558, Japan
Abstract
Chiral hydroxyethyllactones prepared from α-acetyl-γ-butyrolactones by fermenting with baker’s yeast are reduced to give chiral triols.
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■ Asymmetric Michael Addition Reaction of Methyl Phenylthioacetate to 2-Cyclopentenone Catalyzed by Chiral Crown - KotBu Complexes
Shin Aoki, Shigeki Sasaki,and Kenji Koga*
*Faculty of Pharmaceutical Sciences, University of Tokyo, Hongo, Bunkyo-ku, Tokyo 113, Japan
Abstract
Asymmetric Michael addition reaction of methyl phenylthioacetate (12) to 2-cyclopentenone (11) using chiral crown ether - KOt Bu complexes a catalysts is reported. Crown (7) has been found to give 14 of 71 %ee (enantiomeric excess) .
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■ Total Synthesis of (+)-Erysotrine via Asymmetric Diels-Alder Reaction Under Super High Pressure
Yoshisuke Tsuda,* Shinzo Hosoi, Nobuya Katagiri, Chikara Kaneko, and Takehiro Sano
*Faculty of Pharmaceutical Scicences, Kanazawa University, 13-1 Takara-machi, Kanazawa 920-0934, Japan
Abstract
The first total synthesis of (+)-erysotrine in a chiral form was achieved through application of Diels-Alder reaction of a chiral dioxopyrroline with 1-methoxy-3-trimethylsilyloxybutadiene under a 10 Kbar pressure.
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■ A General Formation of Quinone Imines and Quinone Imine Acetals: An Efficient Synthesis of 5-Oxygenated Indoles
Yasuyuki Kita,* Hirofumi Tohma, Masanao Inagaki, and Kenji Hatanaka
*Faculty of Pharmaceutical Sciences, Osaka University, 1-6 Yamadaoka, Toyonaka, Osaka 560-0043, Japan
Abstract
A general and high-yield synthesis of benzoquinone imines and benzoquinone imine monoacetals leading to 5-oxygenated indoles was developed.
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■ Synthesis of Aryl Substituted Epihalohydrin Derivatives
Masaaki Yoshida,* Tetsuro Hide, Masabumi Ohshima, Haruko Sasaki, and Takashi Toda
*Department of Applied Chemistry, Faculty of Engineering, Utsunomiya University, 7-1-2 Yoto, Utsunomiya 321-8585, Japan
Abstract
Aryl substituted epihalohydrin derivatives were synthesized by the dehydrohalogenation of 2,3-dihalo-3-arylpropanol derivatives in the two phase solvent system of aqueous alkali solution and benzene with a phase transfer reagent such as benzyltrimethylammonium chloride.
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■ Synthesis of 1-Alkyl-3-hydroxy-2-phenylazetidines
Takashi Toda,* Michinori Karikomi, Masabumi Ohshima, and Masaaki Yoshida
*Department of Applied Chemistry, Faculty of Engineering, Utsunomiya University, 7-1-2 Yoto, Utsunomiya 321-8585, Japan
Abstract
Several (R *, S *)-1-alkyl-3-hydroxy-2-phenylazetidines (1) were synthesized by the reaction of (R *, R *)-2-(1-bromobenzyl)oxirane (2a) with aliphatic primary amines in good yields. By the reaction of (R *, S * )-2-(1-bromobenzyl)oxirane (2b), only (R *, R *)-2-aminomethyl-3-phenyloxirane (3) was obtained. Also, the reaction of (R *, R *)-2-(1-bromobenzyl)-2-methyloxirane (2c) gave a mixture of (R *, S *)-3-hydroxy-3-methyl-2-phenylazetidine (4) as the major product and (R *, S *)-2-aminomethyl-2-methyl-3-phenyloxirane (5) as the minor product.
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■ A Versatile New Method for Synthesis of Isoquinolines; 6,8-Dihydroxyisoquinoline Derivatives from 6-Methyl-1,3-oxazin-4-ones
Yutaka Yamamoto,* Yasuo Morita, and Osamu Ohmukai
*Tohoku Pharmaceutical University, 4-4-1 Komatsushima, Aoba-ku, Sendai 981-8558, Japan
Abstract
A versatile method for synthesis of isoquinolone derivatives (4a-h) from 2-substituted 6-methyl-4H -1,3-oxazin-4-ones (1a-h) is described. Transformation of 1a-h with diethyl acetonedicarboxylate (2) in the presence of potassium tert-butoxide afforded 6-substituted 3-acetyl-5-ethoxycarbonyl-4-ethoxycarbonylmethylene-2-pyridones (3a-h) in excellent yields. Dieckmann-type cyclization of 3a-h with sodium ethoxide in ethanol produced the corresponding isoquinolone derivatives (4a-h) in good yields, respectively.
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■ Intermolecular Trapping of Vinyl Nitrene Equilibrated with Azirine
Makoto Sakurai, Keiji Noguchi, Kazuaki Isomura,* Ryuichi Tanaka, and Hiroshi Taniguch*i
*Department of Chemical Engineering, Kitakyushu National College of Technology, Shii, Kokuraminami-ku, Kitakyushu 803, Japan
Abstract
Thermal decomposition of 3-azido-1,2-benzo-l,3-cycloheptadiene (1a) gave the fused azirine (2a), which gave pyrrolobenzocycloheptadiene (3a) on heating with dimethyl acetylenedicarboxylate (DMAD). Thermolysis of 1-azidoindene (1b), did not give the azirine, but gave the fused pyrrole (3b) by decomposition in the presence of DMAD. These results provided firm evidence for intermediacy of vinyl nitrenes.
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■ Asymmetric Synthesis of New Non-natural 1β-Methylcarbapenems Bearing Methylthio Group at the C6-Position
Yoshimitsu Nagao,* Takao Abe, Hisashi Shimizu, Toshio Kumagai, and Yoshinori Inoue
*Faculty of Pharmaceutical Sciences, University of Tokushima, Sho-machi, Tokushima 770-8505, Japan
Abstract
The asymmetric total synthesis of new non-natural 1β-methylcarbapenems (1 and 2) has been accomplished starting from optically active C4-substituted azetidin-2-one (4).
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■ Synthesis of a Dodecadeoxyribooligonucleotide Containing a 3'-Thio Analogue of Thymidine Photodimer
Tetsuya Murata, Shogenori Iwai, and Eiko Ohtsuka*
*Faculty of Pharmaceutical Sciences, Hokkaido University, Sapporo 060-0812, Japan
Abstract
3’-Thio analogue of thymidine 3’-phosphate (Tsp) was incorporated into a dodecadeoxyribonucleotide at the 5’-side of dithymidylate to yield dGCACGTspTGCACG. The oligonucleotide was synthesized by the phosphoramidite method and converted to the cis -syn thymine dimer derivative by irradiation with uv, then isolated by high performance liquid chromatography.
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■ Synthetic Connections to the Directed ortho Methalation Reaction. 3,4-Pyridynes from 4-Trialkylsilyl-3-pyridyl Triflates
Masao Tsukazaki and Victor Snieckus*
*Guelph-Waterloo Centre for Graduate Work in Chemistry, University of Waterloo, Waterloo, Ontario, N2L 3G1, Canada
Abstract
4-Trialkylsilyl-3-pyridyl triflates (11a-b), derived from 9 and 12 by directed ortho metalation chemistry, serve as useful precursors of 3,4-pyridynes (6a-b) and lead by cycloaddition and nucleophilic trapping reactions to products (13a-b, 14a-b, 15, 16a-b, and 17a-b).
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■ Synthesis of 2-Aza-4-ketopodophyllotoxin
Hideji Itokawa,* Yukio Hitotsuyanagi, and Koichi Takeya
*Department of Pharmacognosy, School of Pharmacy, Tokyo University of Pharmacy and Life Science, 1432-1 Horinouchi, Hachioji, Tokyo 192-0392, Japan
Abstract
A synthesis of 2-aza-4-ketopodophyllotoxin (7), a key intermediate of 2-azapodophyllotoxin (1), is reported.
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■ Preparation of Some Naphtho[2,3-f]isoindoles
Makhluf J. Haddadin,* Mona S. Samaha, and Antoun B. Hajj-Ubayd
*Department of Chemistry, American University of Beirut, Beirut, Lebanon
Abstract
The preparation of four derivatives of naphtho[2,3-f]isoindole is described. Three of these derivatives are highly reactive dienophiles.
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■ Conversion of the Synthetic Precursor for Ipecac and Corynanthe Alkaloids into Synthetic Intermediates of Quinine Alkaloids and (±)-Dihydroantirhine
Nobuaki Taniguchi, Masataka Ihara, and Keiichiro Fukumoto*
*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan
Abstract
The epimeric mixture of the trans-substituted tetrahydropyran derivatives (1) was transformed to the cis-substituted lactone (6), which was converted into the piperidine (3), the synthetic intermediate of dihydrocinchonine (5a) and dihydrocinchonidine (5b) , and the synthetic precursor (11) of (±)-dihydroantirhine (4) .
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■ An Enantioselective Synthesis of (R)- and (S)-4,5-Dimethyl-4-hexanolides —— Key Intermediates for 2,3-Dihydro-2-isopropyl-2,5-dimethylfuran, a Sex Specific Compounds in Females of the Beetle Hylecoetus dermestoides L.
Hideo Nemoto, Hiroki Ishibashi, and Keiichiro Fukumoto*
*Pharmaceutical Institute, Tohoku University, Aobayama, Sendai 980-8578, Japan
Abstract
Both the enantiomers, (R)- and (S)-4,5-dimethyl-4-hexanolides (11), were synthesized via tandem asymmetric epoxidation and enantiospecific 1,2-rearrangement of cyclopropylideneethanol (7) as a key reaction.
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■ One-Step Synthesis of 2,3-Dihydroanthra[2,3-b]furan-4,11-diones and 1H-Naphth[2,3-f]indole-4,11-diones by [2+3] Photoaddition of 2-Hydroxy- or 2-Amino-1,4-anthracenedione with Cyclic and Acycli Alkenes
Kazuhiro Kobayashi, Sachiko Kujime, and Hiroshi Suginome*
*Organic Synthesis Division, Faculty of Engineering, Hokkaido University, Sapporo 060, Japan
Abstract
A one-step formation of 2,3-dihydroanthra[2,3-b]furan-4,11-diones in 32~78% yields by a [2+3] type regioselective photoaddition of 2-hydroxy-l,4-anthracenedione with a variety of alkenes is reported. An analogous one-step formation of 1H -2,3-dihydronaphth[2,3-f ]indole-4,11-dione in 53% yield by the [2+3] type regioselective photoaddition of 2-amino-1,4-anthracenedione with isobutene is also described. The photoannelation of 2-amino-1,4-anthracenedione with 2-methoxypropene under the same conditions as with isobutene resulted in the formation of 2-methyl-1H-naphth[2,3-f ]indole-4,11-dione (55%) via a spontaneous elimination of methanol from the intially formed [2+3] photoadduct.
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■ Optimized Geometries and Pyramidal Inversion in σ3λ3-Phosphole: A Brief Theoretical Treatment
Alan N. Hughes* and Kenneth E. Edgecombe
*Department of Chemistry, Lakehead University, Thunder Bay, Ontario, P7B 5E1, Canada
Abstract
Optimized geometries and total energies for the pyramidal and planar conformations of σ3λ3-phosphole have been calculated by ab initio methods using the 6-311G* basis set and the GAUSSIAN 86 series of programs. The inversion barrier is calculated to be 24.4 kcal/mol.
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■ The Photocyclization of N-Acyl-2-nitrodiphenylanines to Phenazine N-Oxides: Scope and Mechanism
Elisa Fasani, Silvio Pietra, and Angelo Albini*
*Istituto di Chimica Organica, Università di Torino, via P. Giuria 9, I-10125 Torino, Italy
Abstract
The photocyclization of N -acyl-2-nitrodiphenylamines to phenazine N -oxides is extended to several dinitro derivatives and a pyridine analogue obtaining N -oxides of otherwise difficult access. In the presence of some additives , the reaction takes a different course. Thus, with acids deacylation occurs, with triphenylphosphine a N -phosphoranylidene amine is formed and with 2,6-di-ter -butylphenol the corresponding nitrosodiphenylammine is obtained. A mechanism starting from the nitroamide triplet and involving several discrete intermediates is proposed in order to account for such observations.
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■ Formal Total Synthesis of Eupolauramine
Mieczyslaw Makosza* and Zbigniew Wróbel
*Institute of Organic Chemistry, Polish Academy of Sciences, ul. Kasprzaka 44/52, P.O.Box 58, PL-01-224 Warszawa 42, Poland
Abstract
The key intermediate for eupolauramine synthesis was obtained in a short reaction sequence in which vicarious nucleophilic substitution of hydrogen was the key step.
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■ Synthesis of 3-(2-Amino)benzylidene-2,5-piperazinedione and Its Conversion to 1-Azanaphthalenone and Spiro[indolinepiperazine]dione Derivtives
Yoshiaki Sato, Yoshiharu Nakajima, and Chung-gi Shin*
*Laboratory of Organic Chemistry, Faculty of Technology, Kanagawa University, 3-27-1 Rokkakubashi, Kanagawa-ku, Yokohama 221-8686, Japan
Abstract
Synthesis of 3-(2-amino)benzylidene-2,5-pipe- razinedione and its conversions by photolysis and by treatment with NBS gave 3-amino-1-azanaphthalen-2(H)-one and spiro [indoline-2(3H),2’-piperazine]-3’,6 ’-dione derivatives, respectively.
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■ Two New Ellagitannin Metabolites, Carpinusin and Carpinusin from Carpinus laxiflora
Gen-ichiro Nonaka,* Michiko Akazawa, and Itsuo Nishioka
*Faculty of Pharmaceutical Sciences, Kyushu University, 3-1-1 Maidashi, Higashi-ku, Fukuoka 812-8582, Japan
Abstract
From the fresh leaves of Carpinus laxiflora (Betulaceae), two new hydrolyzable tannins, carpinusin (2) and carpinusnin (3), have been isolated, together with thirteen known hydrolyzable tannins and related compounds, and their structures were elucidated on the basis of physico-chemical evidence.
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■ An Efficient Synthetic Route to γ,δ-Unsaturated Seven-memberd Lactones
Fusao Kido, Abul B. Kazi, Kazuo Yamaji, Michiharu Kato,* and Akira Yoshikoshi
*Institute for Chemical Reaction Science, Tohoku University, Katahira, Aoba-ku, Sendai 980-8577, Japan
Abstract
Treatment of the diazomalonates (9a-d) of 2-phenylthio-3-butenol derivatives with catalytic rhodium acetate resulted in the [2,3]sigmatropic rearrangement of six-membered allylsulfonium ylides to provide γ, δ-unsaturated seven-membered lactones (10a-d) in good yields.
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■ Synthesis of 2-Oxa and 2-Aza Analogs of Pyrrolizidine-3,5-diones (Lukes-Sorm Dilactam)
Tatsuo Nagasaka,* Rie Hakamada, Shin-ichi Kunii, and Fumiko Hamaguchi
*Tokyo University of Pharmacy and Life Science, 1432-1 Horinouchi, Hachioji, Tokyo 192-0392, Japan
Abstract
The synthesis of 2-oxa and 2-aza analogs of pyrrolizidine-3,5-dione (Lukes-Sorm dilactam), which has amnesia reversal activity, is reported. Optically active (+)-2-oxa and (+)-2-aza analogs [ (+)-2 and (+) -3 ] and racemic 2-aza analog and its 1-methoxycarbonyl derivatives [(±) -3 and (±)-13 and -14 ] were prepared from (-)-S -pyroglutamic acid and succinimide, respectively.
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■ The Reactivity of Monocyclic 1,2,3-Triazine
Takashi Itoh, Kazuhiro Nagata, Terumitsu Kaihoh, Mamiko Okada, Chikako Kawabata, Heihachiro Arai, Hidefumi Ohnishi, Kentaro Yamaguchi, Hiroshi Igeta, Akio Ohsawa,* and Yoichi Iitaka
*School of Pharmaceutical Sciences, Showa University, 1-5-8 Hatanodai, Shinagawa-ku, Tokyo 142-8555, Japan
Abstract
The reactivity of unsubstituted 1,2,3-triazine was investigated using
various nucleophilic and electrophilic reagents, molecular orbital calculations, and low temperature nmr measurements.
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■ Oxoammonium Salts. 4 A New Reagent for Phenol Coupling
James M. Bobbitt* and Zhenkun Ma
*Department of Chemistry, University of Connecticut, Storrs, CT 06269-3060, U.S.A.
Abstract
Oxoammonium salts, such as 2,2,6,6-tetra-methyluioeridlne-1-oxonlum tetrafluoroborate, oxidatlvely couple phenols to dihydroxyblphenyls in good yleld. Furthermore, these compounds can be used to dehydrogenate tertiary amines to imrnium salts and to oxidlze certain phenols to quinones.
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■ A Synthesis of 2,2,4-Trisubstituted 2H-Imidazol-5-ones from 3-Cyano-1,1,4-triaryl-2-aza-1,3-dienes
Veneta Dryanska*
*Department of Chemistry, University of Sofia, Sofia 1126, Bulgaria
Abstract
A series of 4-arylmethyl-2,2-diphenyl-2H -imidazol-5-ones (2a -r ) are prepared via intramolecular cyclization from 4-aryl-3-cyano-1,1-diphenyl-2-aza-1,3-butadienes (1a -r) in aq. NaOH - ethanol system.
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■ Reactions of Heterocyclic N-Oxides. The Synthesis of α-Heteroaryl-α-amino Acid Derivatives and Dipeptides
Berta Kotar Jordan, Branko Stanovnik,* and Miha Tisler
*Department of Chemistry, University of Ljubljana, Murnikova 6, P. O. Box537 61000 Ljubljana, Slovenia
Abstract
Heteroaryl substituted oxazolinylidene derivatives (3) and (4) were converted by opening of the oxazolinone ring under hydrolytic conditions, followed by decarboxylation into acylaminomethyl derivatives (5) and (6), with hydrazine hydrate into the corresponding hydrazides (7) , with liquid ammonia under pressure into amides (8), and with amino acids into dipeptides (9-11).
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■ Radioimmunoassay of Iridoid Glucosides: Part 1. General Method for Preparation of the Haptens and the Conjugates with a Protein of This Series of Glucosides
Kenichiro Inoue, Masami Ono, Hirotoshi Nakajima, Ikuko Fijie, Hiroyuki Inouye, and Tetsuro Fujita*
*Faculty of Pharmaceutical Sciences, Kyoto University, 46-29 Yoshida-shimoadachi-machi, Sakyo-ku, Kyoto 606-8501, Japan
Abstract
In order to obtain antibodies specific to three key intermediates, 7-deoxyloganin (1b), 7-deoxy-8-epi-ioganin (2b) and 10-deoxygeniposide (3b), in biosynthesis of iridoid giucosides in behalf of their microdetermination by a radioimmunoassay technique in various plant extracts, we have synthesized, starting with suitable natural iridoid glucosides, three optically pure intermediates from which we in turn prepared their haptens and conjugates to bovine serum albumin.
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■ Synthesis of N-Ethoxycarbonylmethyl Geissman-Waiss Lactone: Unusual Epimerization of α,β-Unsaturated γ-Lactone
Masakazu Tanaka, Takeshi Murakami, Hiroshi Suemune, and Kiyoshi Sakai*
*Faculty of Pharmaceutical Sciences, Kyushu University, 3-1-1 Maidashi, Higashi-ku, Fukuoka 812-8582, Japan
Abstract
N -Ethoxycarbonylmethyl Geissman-Waiss lactone ((±)-2) was easily synthesized from bis-lactone (3), and an unexpected epimerization of γ-butenolactone was observed in the process of asymmetric synthesis of 2.