Special Issue

Tetsuji Kametani's Special Issues, Vol. 30, No. 2, 1990

49 data found. 1 - 30 listed Next Last
Communication | Special issue | Vol 30, No. 2, 1990, pp. 737 - 740
Published online:
DOI: 10.3987/COM-89-S40
Reactions of a Tetrasubstituted Thiocarbonyl Ylide; New Evidence for Two-Step Cycloadditions

Rolf Huisgen* and Grzegorz Mloston

*Institute of Organic Chemistry, University of Munich, Karlstrasse 23, D-80333, München, Germany


Zwitterionic intermediates from aliphatic thiocarbonyl yields and tetrasubstituted acceptor olefins can close the 5-membered ring (thiolane) or the 7-membered ring (ketene imine), undergo rotation, and - shown here - furnish cyclopropane and thione in an intramolecular nucleophilic substitution.

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Communication | Special issue | Vol 30, No. 2, 1990, pp. 741 - 744
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DOI: 10.3987/COM-89-S42
Highly Accelerated Reactions in a Microwave Ovem: Synthesis of Heterocycles

Ajay K. Bose,* Maghar S. Manhas, Malay Ghosh, Vegesna S. Raju, Keiko Tabei, and Zofia Urbancyk-Lipkowska

*Department of Chemistry and Chemical Engineering, Stevens Institute of Technology, Castle Point on the Hudson, Hoboken, NJ 07030, U.S.A.


Efficient synthesis of a wide variety of heterocycles on 0.1 to 200 g scale was conducted in organic solvents in a commercial microwave oven in a few minutes at a low energy level. Erlenmeyer flasks were adequate reaction vessels since neither high pressure nor high temperature were involved. Fast monitoring of synthetic reactions was achieved by tlc separation and transfer of tlc spot material directly to a solids probe of a chemical ionization mass spectrometer. Microwave Oven-induced Reaction Enhancement (MORE) chemistry is not due to thermolysis: one reaction was conducted successfully in a reaction vial encased in a block of ice.

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Communication | Special issue | Vol 30, No. 2, 1990, pp. 745 - 748
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DOI: 10.3987/COM-89-S48
Biocatalytic Preparation of Chiral β-Hydroxy Esters Substituted with Heteroring at γ-position

Katsuyuki Kurumaya, Kazuhiko Takatori, Rieko Isii, and Masahiro Kajiwara*

*Department of Medicinal Chemistry, Meiji Pharmaceutical University, 2-522-1 Noshio, Kiyose, Tokyo 204-8588, Japan


Asymmetric reduction were examined of β-keto esters substituted with dithiane ring at γ-position with microorganism and gave the alcohol with high optical purity. Also the chiral carbinol with furan ring was obtained by the hydrolysis of the corresponding acetate with lipase or baker’s yeast.

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Communication | Special issue | Vol 30, No. 2, 1990, pp. 749 - 752
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DOI: 10.3987/COM-89-S53
Synthesis of 2-Phenyl-2,3,4,5-tetrshydro-1-benzoxepin-5-ones

Toshio Tatsuoka,* Kayoko Imao, Kenji Suzuki, Makoto Shibata, Fumio Satoh, Seiji Miyano, and Kunihiro Sumoto

*Suntory Institute for Biochemical Research, Suntory Co. Ltd., 1-1-1, Wakayamadai, Shimamotocho, Mishimagun, Osaka 618-0024, Japan


A series of 2-phenyl-1-2,3,4,5-tetrahydro-1-benzoxepin-5-ones were synthesized by 2 steps from flavones through 3,4-benzo-5-oxo-2-oxabicyclo[4.1.0]heptanes.

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Communication | Special issue | Vol 30, No. 2, 1990, pp. 753 - 758
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DOI: 10.3987/COM-89-S81
Controlling Factors for the Formation of Pyrrole, Pyridine, and Azepine in Thermal Rearrangement of 2H-Azirines

Masumi Saruwatasi, Kazuaki Isonuma, and Hiroshi Taniguchi*

*Faculty of Engineering, Kyushu University, 6-10-1 Hakozaki, Higashi-ku, Fukuoka 812-8581, Japan


Thermal rearrangement of 2-(cyclohexen-1-yl)- and 2-(cyclopenten-1-yl)-2H-azirines, bearing a methyl or a phenyl group at the 2-position of cycloalkenes, was compared with those of corresponding acyclic and benzofuranylazirines. Suppression of the cyclization into pyrrole in favor of pyridine and azepine formations from the azirines having cyclic unsaturation is explained by the strain of fused 2H-pyrrole and the electronic character of vinyl nitrene intermediates.

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Communication | Special issue | Vol 30, No. 2, 1990, pp. 759 - 764
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DOI: 10.3987/COM-89-S83
Structure Determination of a Violet-Blue Flower Flavonoid, Qurcetin 3-Glucosyl(1→2)gentiobioside from Primula polyantha

Norio Saito, Keiko Yoda, Hideyuki Haruyama, Harumitsu Kuwano, and Toshio Honda*

*Faculty of Pharmaceutical Sciences, Hoshi University, 2-4-41 Ebara, Shinagawa-ku, Tokyo 142-8501, Japan


The chemical structure of quercetin 3-glucosyl(1→2)gentiobioside, isolated from the violet blue flowers of Primura polyantha was determined to be quercetin 3-O-(β-D-glucopyranosyl(1→2)-O-β-D-glucopyranosyl(1→6))-β-D-glucopyranoside unambiguously based on the spectroscopic data.

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Communication | Special issue | Vol 30, No. 2, 1990, pp. 765 - 769
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DOI: 10.3987/COM-89-S87
Response of 2-Lithio-4,5-dihydrofuran — Ketone Adducts to Acid Catalysis

Leo A. Paquette,* David E. Lawhorn, and Christopher A. Teleha

*Evans Chemical Laboratories, The Ohio State University, 120 W. 18th Avenue, Columbus, Ohio 43210, U.S.A.


Tertiary allylic alcohols derived from 1,2-addition of 2-lithio-4,5-dihydrofuran to ketones are shown to be capable of conversion to dimeric spiro-1,4-dioxanes or to monomeric ring-expanded spirocyclic ketones depending upon the conditions of acid catalysis employed.

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Communication | Special issue | Vol 30, No. 2, 1990, pp. 771 - 773
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DOI: 10.3987/COM-89-S93
A Novel Synthesis of Trialkylstannyl- and Silypyridine Derivatives through Diels-Alder Reaction of 6H-1,3-Oxazin-6-ones

Yutaka Yamamoto* and Yasuo Morita

*Faculty of Pharmaceutical Sciences, Tohoku Pharmaceutical University, 4-4-1 Komatsushima, Aoba-ku, Sendai 981-8558, Japan


A novel and convenient method for the synthesis of trimethylstannyl- and silylpyridine derivatives through Diels-Alder reaction of 6H-1,3-oxazin-6-ones with trialkylstannyl- and -silylacetylene derivatives was developed.

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Communication | Special issue | Vol 30, No. 2, 1990, pp. 775 - 778
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DOI: 10.3987/COM-89-S98
A Mild and Rapid 1,2-trans-Glycosidation Method via Benzoyl-protected Glycopyranosyl P,P-Diphenyl-N-(p-toluenesulfonyl)phosphinimidates

Shun-ichi Hashimoto, Takeshi Honda, and Shiro Ikegami*

*Faculty of Pharmaceutical Sciences, Teikyo University, 1091-1, Sagamiko, Kanagawa 199-0195, Japan


A highly efficient 1,2-trans-glycosidation reaction with a range of acid-labile alcohols has been developed by employing benzoyl-protected glycopyranosyl P,P-diphenyl-N-(p-toluenesulfonyl)phosphinimidates as glycosyl donors.

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Communication | Special issue | Vol 30, No. 2, 1990, pp. 779 - 782
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DOI: 10.3987/COM-89-S100
Reinvestigation of the Reaction of 3-Bromo-4-nitroquinoline 1-Oxide with 1-Morpholinocyclohexene

Yutaka Miura, Yasuo Fujimura, Sakae Takaku, and Masatomo Hamana*

*Chugai Pharmaceutical Company, Ltd., 135, 1-Chome Komakado, Gotemba City, shizuoka 412-8513, Japan


Reinvestigation of the reaction of 3-bromo-4-nitroquinoline-1-oxide (2) with 1-morpholinocyclohexene (3) has revealed that the reaction proceeds by a multistep ionic process involving the initial formation of 3-morpholino-4-nitro-2-(2-oxocyclohexyl)quinoline (6) and the subsequent tranformation of 6 into 10-nitro-1,2,3,4-tetrahydrobenzofuro[3,2-b]quinoline (5). Not only 2 reacts with various enamines in the same way, but also 3-bromo-4-nitropyridine N-oxide (7) undergoes the same type of reactions.

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Communication | Special issue | Vol 30, No. 2, 1990, pp. 783 - 787
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DOI: 10.3987/COM-89-S104
Synthwsis of (+)-Galactostatin

Sakae Aoyagi, Satoshi Fujimaki, Naoki Yamazaki, and Chihiro Kibayashi*

*School of Pharmacy, Tokyo University of Pharmacy and Life Science, 1432-1 Horinouchi, Hachioji, Tokyo 192-0392, Japan


The chiral synthesis of (+)-galactostatin (3), a new β-galactosidase inhibitor, has been achieved, in which the key step involved a diastereoselective epoxidation of the allylic alcohol (4) derived from L-tartaric acid.

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Communication | Special issue | Vol 30, No. 2, 1990, pp. 789 - 793
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DOI: 10.3987/COM-89-S107
The Nitrogenated Allylic System as an Intramolecular Nucleophile: A New Route to Pyrazoles

Takefumi Momose,* Naoki Toyooka, Takashi Ikuta, and Hironobu Yanagino

*Faculty of Pharmaceutical Sciences, Toyama Medical and Pharmaceutical University, 2630 Sugitani, Toyama, Toyama 930-0194, Japan


A new route to pyrazoles via the cyclization of N-allyl-N-nitrosoamides is described.

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Communication | Special issue | Vol 30, No. 2, 1990, pp. 795 - 798
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DOI: 10.3987/COM-89-S108
Lignans and Sesquiterpenoids asa PAF Antagonists

Satoshi Iwakami, Yutaka Ebizuka, and Ushio Sankawa*

*Faculty of Pharmaceutical Sciences, University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan


Some lignans and sesquiterpenes were found to have potent PAF antagonist activities. In particular, 6-O-angeloyl- and 6-O-senecioylplenolins (18,19) are the most potent and specific PAF antagonists found in this study.

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Communication | Special issue | Vol 30, No. 2, 1990, pp. 799 - 812
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DOI: 10.3987/COM-89-S109
2-(Heteroatom-substituted)methyl Penems. IV. Oxygen Derivatives

Marco Alpegiani, Angelo Bedeschi, Franco Giudici, Ettore Perrone, Giuseppina Visentin, Franco Zarini, and Giovanni Franceschi*

*Ricerca&Sviluppo Chimico, Farmitalia Carlo Erba SpA, Via dei Gracchi 35, 20146 Milano, Italy


The synthesis of "2-CH2X" penems wherein X is an oxygen atom partof an acyloxy, N-substituted carbamoyloxy, alkoxy or aryloxy residue is described, with emphasis to procedures which exploit a common 2-hydroxymethylpenem precursor. Correlations are attempted between chemical structure of the X moiety and antibacterial activity of obtained compounds.

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Communication | Special issue | Vol 30, No. 2, 1990, pp. 813 - 816
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DOI: 10.3987/COM-89-S110
Synthesis of Oxasteroidal Skeletons by (4+2) Type Cycloaddition of Coumarin and 6-Methyl-2-pyrone with Siloxydienes Mediated by t-Butyldinethylsilyl Triflate

Yong-gyun Lee, Yukinori Utsumi, Katsuo Ohkata, and Kin-ya Akiba*

*Department of Chemistry, Faculty of Science, Hiroshima University, 1-3-1 Kagamiyama, Higashi-Hiroshima, Hiroshima 739-8526, Japan


A new simple methodology is described for the preparation of oxasteroidal skeletons containing a lactone ring via cycloaddition of 2-t-butyldimethylsiloxypyrylium triflate (2a,b) with siloxydienes (3).

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Paper | Special issue | Vol 30, No. 2, 1990, pp. 817 - 830
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DOI: 10.3987/COM-89-4966
Versatile Methods of Synthesis of 5 to 8-Membered Ring N-Heterocycles via Intramolectlar Cycloadditons of Allylamines

K. M. Lokanatha Rai and Alfred Hassner*

*Department of Chemistry, Bar-Ilan University, Ramat-Gan 52900, Israel


N-Tosylallylamines or homoallylamines were monoalkylated with dibromoalkanes to produce bromoalkylamines 3 or 7. The latter were converted to unsaturated nitro derivatives which, via nitrile oxides, underwent intramolecular cycloaddition of the bromo derivatives 3 either via azides to fused triazolines or by free radical reaction to pyrrolidines is also described. These reactions provide an entry into functionalized 5 to 8 membered ring heterocycles.

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Paper | Special issue | Vol 30, No. 2, 1990, pp. 831 - 838
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DOI: 10.3987/COM-89-S31
The Eastman’s Reaction Revisited

Benito Alcaide, Carmen Domínguez, Aurelio G. Csákÿ, and Joaquín Plumet*

*Departamento de Química Orgánica, Facultad de Química, Universidad Complutense de Madridas, Ciudad Universitaria, E-28040 Madrid, Spain


Several previously unknown 3-acyl-5-alkyl-1-arylpyrazoles, differently functionalized in the 3- and 5- side chains, have been synthesized from appropriate 2,5-disubstituted furans by their reaction with p-nitrobenzenediazonium salts.

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Paper | Special issue | Vol 30, No. 2, 1990, pp. 839 - 853
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DOI: 10.3987/COM-89-S37
Preparation of N-Alkadienyl N-E-2-Arylethenylcarbamates via Sulfoxide Elimination in a Synthetic Approach to Lycorine

Michael E. Jung* and Steven J. Miller

*Department of Chemistry, University of California, Irvine, Irvine, California 92697, U.S.A.


N-E-2-Arylethenylcarbamates have been prepared in good yields from N-[2-(phenylthio)-2-arylethyl]carbamates via sulfoxide elimination towards nitrogen.

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Paper | Special issue | Vol 30, No. 2, 1990, pp. 855 - 862
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DOI: 10.3987/COM-89-S62
Recent Work on the Synthesis of Phosphonate-containing, Bone-active Heterocycles

Frank H. Ebetino,* Charles R. Degenhardt, Laura A. Jamieson, and Don C. Burdsall

*Norwich Eaton Pharmaceuticals, Inc., Procter and Gamble Company, P. O. box 191, Norwich, New York 13815, U.S.A.


New approaches to the design and synthesis of bone antiresorptive phosphonates have led to the discovery of the cyclic bisphosphonate series and the phosphonoalkylphosphinate heterocyclic series. The latter class, which offers substrates for interesting dianion chemistry, has ben shown to include effective bone-active isosteres of the well known bisphosphonates.

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Paper | Special issue | Vol 30, No. 2, 1990, pp. 863 - 869
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DOI: 10.3987/COM-89-S68
The Synthesis of Carbapenem and Carbacephem Derivatives by a Combination of 4CC with the Chemistry of Oxazoles and N-Boc-carbonamides

Gebhard Neyer, Josef Achatz, Bernhard Danzer, and Ivar Ugi*

*Organisch-Chemisches Institut der Techmisches, Universität München, Münvhen, D-8046 Garching, Germany


A synthetic approach to carbapenem and carbacephem derivatives is described. It is based on the formation of the N-carboxymethyl-β-lactam system by a four component condensation, the cleavage of a carbonamide via the N-Boc-carbonamides and esters, and the masking of a carboxyl group as its 4,5-diphenyloxazolyl derivative that is convertible to an N,N-dibenzoylamide by photooxidation.

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Paper | Special issue | Vol 30, No. 2, 1990, pp. 871 - 874
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DOI: 10.3987/COM-89-S72
Reduction of N-Oxide with Baker’s Yeast

Mitsuhiro Takeshita* and Sachiko Yoshida

*Tohoku Pharmaceutical University, 4-4-1 Komatsushima, Aoba-ku, Sendai 981-8558, Japan


Reduction of N-oxides with baker’s yeast has been examines. In the reduction of acetylpyridine N-oxides, selective reduction takes place to give chiral pyridylethanol N-oxides.

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Paper | Special issue | Vol 30, No. 2, 1990, pp. 875 - 884
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DOI: 10.3987/COM-89-S75
Syntheses of a Naturally Occurring Hydroxamic Acid and Its Analogues

Akihiro Ohta,* Nobuhiro Takahashi, Yasuko Shirokoma, Kayo Yuasa, Teruo Kurihara, and Hiroshi Miyamae

*Tokyo University of Pharmacy and Life Science, 1432-1 Horinouchi, Hachioji, Tokyo 192-0392, Japan


A naturally occurring cyclic hydroxamic acid, isolated from Pseudomonas species, and its analogues were synthesized via six steps starting from 2-hydroxy-3-methoxypyridine. The antimicrobial activity of the synthesized compounds is described.

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Paper | Special issue | Vol 30, No. 2, 1990, pp. 885 - 896
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DOI: 10.3987/COM-89-S77
2-Oxotetrahydro-1,3-oxazine: A Useful Interamediate for the Preparation of Tetrahydropyridine, Indolizidine, and Quinolizidine Skeletons

Takushi Kurihara,* Yoshitaka Matsubara, Hirotaka Osaki, Sinya Harusawa, and Ryuji Yoneda

*Faculty of Pharmaceutical Science, Osaka University of Pharmaceutical Sciences, 4-20-1 Nasahara, Takatsuki, Osaka 569-1094, Japan


Conversion of 2-oxotetrahydro-1,3-oxazines into tetrahydropyridines was applied to the synthesis of indolizidine and quinolizidine alkaloids.

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Paper | Special issue | Vol 30, No. 2, 1990, pp. 897 - 904
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DOI: 10.3987/COM-89-S78
Studies on the Constituents of Beesia calthaefolia, and Souliea vaginata. III. Beesioside IV, a Cyclolampstanol Xyloside from the Rhizomes of B. calthaefolia and S. vaginata

Nobuko Sakurai, Teruo Goto, Masahiro Nagai, Takao Inoue,* and Peigen Xiao

*Hoshi University, 2-4-41 Ebara, Shinagawa-ku, Tokyo 142-8501, Japan


A new triterpenol xyloside, beesioside IV, an amorphous powder, [α]D-11.1°, C37H58O11·3/2H2O from the dried rhizomes of Beesia calthaefolis Maxim. and Souliea vaginata (Maxim.) Franch. (both Ranunculaceas) was identified as (20S,24S)-15α-acetoxy-16β,24;20,24-diepoxy-9,19-cyclolanostane-3β,12α,25-triol 3-O-β-D-xylopyranoside on the basis of chemical and physicochemical evidence.

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Paper | Special issue | Vol 30, No. 2, 1990, pp. 905 - 908
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DOI: 10.3987/COM-89-S82
An Easy Synthesis of 4-Alkylthioindoles

Masayuki Murase, Toshihiro Hosaka, and Seisho Tobinaga*

*Showa Pharmaceutical University, 3-3165, Higashi-tamagawagakuen, Machida, Tokyo 194-8543, Japan


4-Alkylthio-indoles 7 and 9 were synthesized from 4-thioxo-4,5,6,7-tetrahydroindole (5) in one pot reaction.

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Paper | Special issue | Vol 30, No. 2, 1990, pp. 909 - 927
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DOI: 10.3987/COM-89-S84
Concerning the Intermediacy of Monocyclic β-Lactams in Penicillin Biosynthesis: Synthesis and Attempted Bioconversion of Seco-isopenicillin N

A. Ian Scott,* Ramaswamy Shankaranarayan, and Sung-Kee Chung

*Center for Biological NMR, Department of Chemistry, Texas A & M University, College Station, Texas 77843-3255, U.S.A.


The title compound (3a) was synthesized as its dimer by the skeletal rearrangement of protected isopenicillin N-sulfoxide, hydrogenation, hydrolysis of the thiazoline ring, oxidative dimerization and deprotection. The reductive conversion of the dimer to monomer (3a) was clearly demonstrated. Seco-isopenicillin N (3a) gave no bioactive products on incubation with cell-free systems from either Cephalosporium acremonium or Streptomyces clavuligerus.

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Paper | Special issue | Vol 30, No. 2, 1990, pp. 929 - 937
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DOI: 10.3987/COM-89-S86
Nickel-catalyzed Reactions of Thiazoles, Isoxazoles, Oxazolines and Thiazolines with Grignard Reagents

Ernest Wenkert* and Aili Han

*Department of Medicine, University of California, San Diego, 9500 Gilman Drive, La Jolla, CA 92093-0682, U.S.A.


Grignard reagents convert thiazoles, isoxazoles, oxazolines and thiazolines into N-vinylimines, β-amino-α,β-unsaturated ketones, tetrahydrooxazoles and tetrahydrothiazoles, respectively, under the influence of phosphine-ligated nickel species. The reaction characteristics and the uncatalyzed reactions are described.

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Paper | Special issue | Vol 30, No. 2, 1990, pp. 939 - 947
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DOI: 10.3987/COM-89-S89
Photoinduced Generation of Glycosyl Cations from Thioglycosides

Gary W. Griffin, Nayanie C. Bandara, Margaret A. Clarke, Wing-Sum Tsang, Per J. Garegg,* S. Oscarson, and B. Azmy Silwanis

*Department of Organic Chemistry, Arrhenius Laboratory, University of Stockholm, SE-10691 Stockholm, Sweden


Photochemically induced clevage of thioaryl β-D-glucopyranosides using 1,4-dicyanonaphthalene as an electron-transfer agent, produces glycosyl cations potentially useful in glycosylation reactions.

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Paper | Special issue | Vol 30, No. 2, 1990, pp. 949 - 956
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DOI: 10.3987/COM-89-S92
Mass Spectrometry of Organogermanium Compounds. Fragmentation Process of 1-Germacyclohexane and Their Methyl Derivatives

Katsumi Tanaka and Yoshito Takeuchi*

*Department of Chemistry, The College of Arts & Sciences, The University of Tokyo, Komaba, Meguro-ku, Tokyo 153, Japan


The mass spectrometric fragmentation caused by electron impact of germacyclohexane, 3-methyl- and 4-methyl derivatives and their deuteratated species were analyzed. Intially the clevage of Ge-C bond took place, followed by loss of hydrocarbon moieties. The whole fragmentation processes can be explained by the combination of elimination of hydrocarbon moiety(neutral and radical) and hydrogen transfer(McLafferty rearrangement). The base peaks were at m/z 74 (germanium cation radical) in contrast to that of 1,1-dimethyl-1-germacyclohexanes at m/z 89.

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Paper | Special issue | Vol 30, No. 2, 1990, pp. 957 - 962
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DOI: 10.3987/COM-89-S94
Synthesis of Heteroarylquinolines by the Photolysis of 2-, 3-, and 4-Iodoquinolines

Kazue Ohkura, Koh-ichi Seki,* Masanao Terashima, and Yuichi Kanaoka

*Faculty of Pharmaceutical Scicences, Higashinihonngakuen University, 1757 Kanazawa, Toubetu-cho, Ishikari-gun, Hokkaodo 061-0212, Japan


Photoreaction of 2-, 3-, and 4-iodoquinolines with five membered heterocycles (i.e. 1-methylpyrrole, pyrrole, furan and thiophene) afforded the corresponding n-(2-heteroaryl)quinolines (n=2,3,4) in appreciable yields.

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49 data found. 1 - 30 listed Next Last