Special Issue

Teruaki Mukaiyama's Special Issues, Vol. 52, No. 2, 2000

56 data found. 31 - 56 listedFirst Previous
Paper | Special issue | Vol 52, No. 2, 2000, pp. 693 - 705
Published online:
DOI: 10.3987/COM-99-S69
Epoxidation of Alkenes with H2O2 Generated in situ from Alcohols and Molecular Oxygen Using N-Hydroxyphthalimide and Hexafluoroacetone as Catalysts

Takahiro Iwahama, Satoshi Sakaguchi, and Yasutaka Ishii*

*Department of Applied Chemistry, Faculty of Engineering, Kansai University, Suita, Osaka 564-8680, Japan


A new epoxidation method of olefins with hydrogen peroxide and/or α-hydroxy hydroperoxide which are generated in situ from an alcohol and molecular oxygen was developed. A variety of alkenes were smoothly epoxidized with molecular oxygen in the presence of an alcohol under the influence of hexafluoroacetone (HFA) and N-hydroxyphthalimide (NHPI) as catalysts. The reaction involves the formation of α-hydroxy hydroperoxide and/or hydrogen peroxide derived from 1-phenylethanol and dioxygen by the action of NHPI and the active oxygen transfer from these hydroperoxides to HFA, giving 2-hydroperoxyhexafluoro-2-propanol which serves as the actual epoxidizing agent.

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Paper | Special issue | Vol 52, No. 2, 2000, pp. 707 - 717
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DOI: 10.3987/COM-99-S74
Novel Synthesis of 1-Fluoro-1-silyloxiranes Using Bromo(tert-butyldimethylsilyl)fluoromethyllithium and Carbonyl Compounds

Masaki Shimizu,* Takeshi Hata, and Tamejiro Hiyama

*Department of Material Chemistry, Graduate School of Engineering, Kyoto University, Yoshida, Sakyou-ku, Kyoto 606-8501, Japan


Treatment of dibromo(tert-butyldimethylsilyl)fluoro-methane with BuLi in THF at -78 °C generated bromo(tert-butyldimethylsilyl)fluoromethyllithium, which reacted with aldehydes and ketones to give 1-fluoro-1-silyloxiranes in good yields. Alkylation of the carbenoid was also achieved efficiently.

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Paper | Special issue | Vol 52, No. 2, 2000, pp. 719 - 732
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DOI: 10.3987/COM-99-S78
Synthesis of Optically Pure 1-(2-Pyridinyl)ethylamine and 4-(2-Pyridinyl)-1,3-oxazolin-2-one

Jun'ichi Uenishi,* Takao Hiraoka, Kyoko Yuyama, and Osamu Yonemitsu

*Kyoto Pharmaceutical University, Misasagi-Shichonocho, Yamashina, Kyoto 607-8414, Japan


Several (R)-1-(2-pyridinyl)ethylamines (4) were prepared from (S)-1-(2-pyridinyl)ethanols (1) with complete inversion of the chiral center. Substitution of (S)-1-(2-pyridinyl)ethyl methanesulfonate (2) with sodium azide gave (R)-1-(2-pyridinyl)ethyl azide (3) stereospecifically, and reduction of the azide afforded the corresponding amine (4) in good yield. When optically pure 2-silyloxy-1-(2-piridinyl)ethanol was used, 2-silyloxy-1-(2-pyridinyl)ethylamine was obtained, and this was converted to optically pure pyridine-substituted 1,3-oxazolidin-2-one at the 4-position.

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Paper | Special issue | Vol 52, No. 2, 2000, pp. 733 - 749
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DOI: 10.3987/COM-99-S83
Diastereo- and Enantioselective Synthesis of γ- and δ-Lactams Bearing a Propionic Acid α-Side-Chain via Michael Addition of N-Dialkylamino Lactams to Enoates

Dieter Enders,* Pascal Teschner, and Gerhard Raabe

*Institut für Organische Chemie, Rheinisch-Westfälische, Technische Hochschule, Professor-Pirlet-Strasse 1, D-52074 Aachen, Germany


γ- and- δ-Lactams [(R,R)-5a-e] bearing a propionic acid α-side-chain were synthesized in good overall yields (38 - 58 %, two steps) and diastereo- and enantiomeric excesses (de = > 96%, ee = 90 - > 96%) by 1,4-addition of metalated N-dialkylamino lactarns [(S)-2a,b] to enoate Michael acceptors (3) followed by saponification of the ester group and subsequent removal of the chiral auxiliary by reductive cleavage of the N-N-bond with lithium in liquid ammonia.

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Paper | Special issue | Vol 52, No. 2, 2000, pp. 751 - 760
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DOI: 10.3987/COM-99-S84
Formation and Reaction of o-Quinol Acetates of N-Acyl- and N-Methanesulfonyl-1,2,3,4-tetrahydro-6-methoxyisoquinolin-7-ols

Osamu Hoshino,* Masaji Suzuki, and Hiromichi Ogasawara

*Faculty of Pharmaceutical Sciences, Science University of Tokyo, 12, Ichigaya Funagawara-machi, Shinjuku-ku, Tokyo 162-0826, Japan


Oxidation of N-formyl-, N-acetyl-, N-ethoxycarbonyl-, and N-methanesulfonyl-1,2,3,4-tetrahydro-6-methoxyisoquinolin-7-ols (1b-e) with lead tetraacetate in dichloromethane (CH2Cl2) produced quantitatively corresponding o-quinol acetates (2b-e), treatment of which with trifluoroacetic acid in CH2Cl2 at 0°C for a few minutes afforded corresponding N-acyl- and N-methanesulfonyl-wilsonirines (4b-e) and N-acyl- and N-methanesulfonylnorsebiferines (5b-e). When the reaction was carried out at room temperature, o-quinol acetates (2d,e) of N-ethoxycarbonyl and N-methanesulfonyl congeners (1d,e) gave 1-[2-(ethoxycarbonylamino)ethyl]- and 1-[2-(methanesulfonylamino)ethyl]-4-hydroxy-3,6,7-trimethoxyphenanthrenes (8d,e).

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Paper | Special issue | Vol 52, No. 2, 2000, pp. 761 - 774
Published online:
DOI: 10.3987/COM-99-S86
New Syntheses of Tricyclic Thiophenes and Cyclic Tetrathiophenes Using Transition-Metal-catalyzed Cyclization

S. M. Humayun Kabir, Mami Miura, Shigeru Sasaki, Genta Harada, Yoshiyuki Kuwatani, Masato Yoshida, and Masahiko Iyoda*

*Department of Chemistry, Graduate School of Science, Tokyo Metropolitan University, Hachioji, Tokyo 192-0397, Japan


New synthetic methods for polycyclic thiophenes were developed. Thus, dithienothiophenes, cyclopentadithiophene, silacyclopentadithiophenes, and cyclooctatetrathiophenes were synthesized in moderate to good yields by using the CuCl2-mediated cyclization of organocopper(I) and organozinc intermediates prepared from dilithio-derivatives with CuCN or ZnCl2, respectively. A direct cyclization of brornothiophene derivatives with hexamethylditin in the presence of tetrakis(triphenylphosphine)palladium(0) also gave dithienothiophenes, cyclopenta-dithiophenes, and silacyclopentadithiophenes in good yields.

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Paper | Special issue | Vol 52, No. 2, 2000, pp. 775 - 798
Published online:
DOI: 10.3987/COM-99-8612
Synthesis of Neosaponins Carrying Oligosaccharides from Natural Products

Tsuyoshi Ikeda, Junei Kinjo, Tetsuya Kajimoto, and Toshihiro Nohara*

*Faculty of Pharmaceutical Sciences, Kumamoto University, 5-1 Oe-hon-machi, Kumamoto 862-0973, Japan


The natural oligosaccharide moieties, α-L-rhamnopyranosyl-(1→2)-β-D-galactopyranosyl-(1→2)-β-D-glucuronopyranose (fabatriose) and α-L-arabinofuranosyl-(1→4)-[β-D-glucopyranosyl-(1→3)]-α-L-rhamnopyranosyl-(1→2)-β-D- glucopyranose (mimosatetraose), were respectively cleaved from soyasaponin I and julibrosides, and were linked to appropriate aglycones to give neosaponins. The cytotoxicity and hepatoprotective activity of the obtained neosaponins were assayed. The transglycosidation method developed here could be applied to synthesize novel bioactive glycosides.

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Paper | Special issue | Vol 52, No. 2, 2000, pp. 799 - 810
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DOI: 10.3987/COM-99-S89
Some Properties of Cyclic Phosphoramidites and Their Phosphites: Phosphitylation, Ester Exchange, and Hydrolysis

Yutaka Watanabe* and Shin-ichi Maehara

*Department of Applied Chemistry, Faculty of Engineering, Ehime University, 3 Bunkyo-cho, Matsuyama, 790-8577 Ehime, Japan


Phosphorylation of diols using sterically bulky cyclic phosphoramidites was performed in a good selectivity. Their phosphite derivatives underwent tetrazole-catalyzed hydrolysis and transesterification. The reaction was shown to proceed via a phosphorane intermediate by NMR analysis.

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Paper | Special issue | Vol 52, No. 2, 2000, pp. 811 - 817
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DOI: 10.3987/COM-99-S90
15N Nmr Study of Toxoflavin and Fervenulin

Hiroyuki Koshino,* Yoshiki Kono, Katsuyoshi Yoneyama, and Jun Uzawa

*The Institute of Physical and Chemical Research (RIKEN), Wako, Saitama 351-0198, Japan


15N NMR chemical shifts and the long-range 1H- 15N coupling constant values of toxoflavin and fervenulin are reported. Complete 15N NMR assignments were established by 2D 1H-15N PFG-HMBC experimental data including four-bond correlations at natural abundance.

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Paper | Special issue | Vol 52, No. 2, 2000, pp. 819 - 826
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DOI: 10.3987/COM-99-S92
One-Step Synthesis of Disaccharide Mimetics via Tandem Rearrangement of Unsaturated Disaccharides

Alan James Pearce, Jean-Maurice Mallet, and Pierre Sinaÿ*

*École Normale Supérieure, Département de Chimie, associé au CNRS, 24 rue Lhomond, 75231 Paris Cedex 05, France


The unsaturated thioglycoside disaccharide (4) undergoes stereoselective tandem reductive rearrangement with TIBAL (triisobutylaluminium) to afford the (1→4) ether-linked disaccharide mimetics (1-3).

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Paper | Special issue | Vol 52, No. 2, 2000, pp. 827 - 843
Published online:
DOI: 10.3987/COM-99-S93
Reactivity Range of a Chiral 1,3-Oxazolidine-2-thione Obtained from Vegetable Source through Chemo-enzymatic Processing

David Gueyrard, Valérie Grumel, Onofrio Leoni, Sandro Palmieri, and Patrick Rollin*

*Institut de Chimie Organique et Analytique, Université d'Orléans, BP 6759, F-45067 Orléans Cédex 2, France


Original chemo-enzymatic processing of epi-progoitrin (1), a glucosinolate extracted from crambe presscake, produces (5R)-5-vinyl-1,3-oxazolidine-2-thione (2) in enantiomerically pure form. The reactivity range of this chiron is investigated.

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Paper | Special issue | Vol 52, No. 2, 2000, pp. 845 - 851
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DOI: 10.3987/COM-99-S94
Synthesis of 3-(2-Oxo-2H-pyranyl-3) Substituted Lactic Acid Derivatives

Marko Skof, Jurij Svete,* and Branko Stanovnik*

*Faculty of Chemistry and Chemical Technology, University of Ljubljana, Askerceva 5, 1000 Ljubljana, Slovenia


(S)-3-[(E)-Dirnethylarninornethylidene]-5-(methoxycarbonyl)tetrahydro-furan-2-one (3) was transformed in one step with various C,O-dinucleophiles (4-13) into the corresponding 3-(2-oxo-2H-pyranyl-3)-2-hydroxypropanoates (14-23).

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Paper | Special issue | Vol 52, No. 2, 2000, pp. 853 - 862
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DOI: 10.3987/COM-99-S96
Diastereoselective Synthesis of 2-Alkyl-1,2,3,4-tetrahydroquinolin-3-ols — An Example of Diastereoconversion of α-Alkyl Epoxides

Martin Kratzel* and Romana Hiessböck

*Institut für Pharmazeutische Chemie, Universität Wien, Pharmaziezentrum, Althanstrasse 14 A-1090 Wien, Austria


The efficient synthesis of both diastereomers of 2-alkyl-1,2,3,4-tetrahydroquinolin-3-ols, representing rigid 1,2-amino alcohols, is outlined applying a diastereoconversion approach. The relative configuration of the title compounds is supported by the unequivocal stereochemical course of the reactions used.

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Paper | Special issue | Vol 52, No. 2, 2000, pp. 863 - 866
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DOI: 10.3987/COM-99-S97
Cyclic Anhydrides Formed from 1,12-Dimethylbenzo[c]phenanthrene-5,8-dicarboxylic Acid and1,3-Benzene-dicarboxylic Acids

Hitoshi Okubo and Masahiko Yamaguchi*

*Departmenr of Organic Chemistry, Graduate School of Pharmaceutical Sciences, Tohoku University, Aobayama, Sendai 980-8578, Japan


Optically active 1,12-dimethylbenzo[c]phenanthrene-5,8-dicarboxylic acid and 1,3-benzenedicarboxylic acids were converted to cyclic anhydrides with trimeric and/or tetrameric structure.

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Paper | Special issue | Vol 52, No. 2, 2000, pp. 867 - 874
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DOI: 10.3987/COM-99-S98
Photocycloaddition of 6-Chloro-1,3-dimethyluracil to Olefins

Kazue Ohkura, Hideaki Nakamura, Hajime Takahashi, and Koh-ichi Seki*

*Faculty of Pharmaceutical Sciences, Health Sciences University of Hokkaido, Ishikari-Tobetsu, Hokkaido 061-0293, Japan


Photoreaction of 6-chloro-1,3-dimethyluracil (6-ClDMU) with olefins having alkyl, alkoxy, and vinyl groups in acetone afforded the corresponding cyclobutapyrimidine derivatives with head-to-tail regiochemistry in appreciable yields, while the reaction with olefins bearing electron withdrawing groups gave no cycloadduct. Similar Photolysis of 6-ClDMU with phenylacetylene gave [2+2] cycloadduts, 3,5-diaza[4.2.0]oct-7-enes and diphenylquinazolines.

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Paper | Special issue | Vol 52, No. 2, 2000, pp. 875 - 883
Published online:
DOI: 10.3987/COM-99-S102
Double Stereodifferentiation in Intramolecular C-H Insertion Reaction toward the Synthesis of 1β-Methylcarbapenem Antibiotics

Masahiro Anada, Shinji Kitagaki, and Shunichi Hashimoto*

*Graduate School of Pharmaceutical Sciences, Hokkaido University, Sapporo 060-0812, Japan


A double asymmetric induction in intramolecular C-H insertion reaction of chiral, non-racemic α-diazo amides has been explored with the aid of dirhodium(II) tetrakis[N-phthaloyl-(R)- or (S)-phenylalaninate], Rh2(R- or S-PTPA)4, as a homochiral catalyst. The combination of α-methoxycarbonyl-α-diazoacetamide (13) with Rh2(S-PTPA)4 provides an 85:15 mixture of the desired 3-oxa-1-azabicyclo[4.2.0]octane derivative (14) and its diastereomer (15), which, upon reduction with LiBH4 and subsequent ready separation, leads to a key intermediate for the synthesis of 1β-methylcarbapenem antibiotics. Doyle-Taber’s C-H insertion model coupled with the solid state structure of Rh2(S-PTPA)4 confirms the observed diastereomer preference.

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Paper | Special issue | Vol 52, No. 2, 2000, pp. 885 - 895
Published online:
DOI: 10.3987/COM-99-S108
A New Synthetic Route to 1,3-Oxazolidines via Palladium-catalyzed Regioselective [3+2] Cycloaddition of Vinylic Oxiranes with Imines

Jae-Goo Shim and Yoshinori Yamamoto*

*Department of Chemistry, Graduate School of Science, Tohoku University, Aobayama, Sendai 980-8578, Japan


Palladium-catalyzed intermolecular reaction of imines (1) with vinylic oxiranes (2) gives the regioselective [3+2] cvcioaddition products, 1,3-oxazolidine derivatives (3), in good to cxcellent yields. The present reaction permits the use of uncoventional starting materials (imines and vinylic oxiranes)for the synthesis of 1,3-oxazolidines (3).

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Paper | Special issue | Vol 52, No. 2, 2000, pp. 897 - 904
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DOI: 10.3987/COM-99-S110
Reactivities of Gibberellins with a Cationic Exchange Resin, Dowex-50W

Hideharu Seto,* Hideki Hayasaka, Hiroyuki Koshino, Shozo Fujioka, and Shigeo Yoshida

*The Institute of Physical and Chemical Research (RIKEN), Hirosawa 2-1, Wako-shi, Saitama 351-0198, Japan


A cationic exchange resin containing sulfonic acid functional groups, Dowex-50W, controlled the reactions of gibberellins (GAs) catalyzed by acid: by optimizing the reaction temperature and solvent, GA1 (1) furnished gibberellin C (7) quantitatively, while GA4 (2) gave endo-GA4 (10) or 16-O-methylGA2 (12) in moderate to good yields, respectively; in a refluxing methanol, GA3 methyl ester (14) gave triene carboxylic acid (15) (47%), iso-GA3 methyl ester (16) (22%) and diene carboxylic acid (17) (11%). The formation of 15 and 16 was explained by a reaction mechanism via a common intermediate, 2β,3β-epoxide (18).

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Note | Special issue | Vol 52, No. 2, 2000, pp. 905 - 910
Published online:
DOI: 10.3987/COM-99-S58
Improved Synthesis of 1-Adamantylphosphine and Its Use in the Synthesis of Cyclicphosphines Containing 1-Adamantyl Group

Atsushi Ohashi, Satoru Matsukawa, and Tsuneo Imamoto*

*Department of Chemistry, Faculty of Science, Chiba University, 1-33 Yayoi-cho, Inage-ku, Chiba 263-8522, Japan


1-Adamantyiphosphine (1) was easily synthesized from 1-adarnantylmagnesium bromide. Several new cyclic trialkyiphosphines bearing 1-adamantyl group were prepared from compound (1).

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Note | Special issue | Vol 52, No. 2, 2000, pp. 911 - 920
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DOI: 10.3987/COM-99-S61
Synthesis of Quinoxaline Derivatives Bearing the Styryl and Phenylethynyl Groups and Application to a Fluorescence Derivatization Reagent

Akira Katoh,* Tohru Yoshida, and Junko Ohkanda

*Department of Industrial Chemistry, Faculty of Engineering, Seikei University, Musashino-shi, Tokyo 180-8633, Japan


The cross-coupling of 2-chloro-6-methoxycarbonyl-3-methylquinoxaline (2) and 3-chloro-7-methoxy-1-methylquinoxalin-2(1H)-one (7) with phenylacetylene in the presence of Pd(PPh3)4 gave 6-methoxycarbonyl-3-methyl-2-phenylethynylquinoxaline (3) and 7-methoxy-1-methyl-3-(4-methoxycarbonyl)-phenylethynylquinoxalin-2(1H)-one (9), respectively. Compounds (3 and 9) were further converted into the corresponding olefinic compounds, 6-methoxvcarbonyl-3-methyl-2-stvrylquinoxaline (4) and 7-methoxy-1-methyl-3-(4-methoxycarbonyl)-styrylquinoxalin-2(1H)-one (10), by partial hydrogenation on palladium catalysts such as Lindlar catalyst and Pd/BaSO4-quinoline, but the conformation of the resulting olefins was unexpectedly E-form. These quinoxaline derivatives showed fluorescent emission bands at a range from 398 to 467 nm in MeCN when the excitation wavelength of 353-405 nm was applied. Further, 3-(4-chlorocarbonyl)-phenylethynyl-7-methoxy-1-methylquinoxalin-2(1H)-one (12) was demonstrated to be applicable to a fluorescence derivatization reagent for amines.

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Note | Special issue | Vol 52, No. 2, 2000, pp. 921 - 928
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DOI: 10.3987/COM-99-S65
Syntheses of Partial Structures of Glycosyl Phosphatidylinositol Anchor

Takashi Yamanoi,* Junichi Inagaki, Mamoru Mizuno, Katsuko Yamashita, and Toshiyuki Inazu*

*The Noguchi Institute, 1-8-1, Kaga, Itabashi-ku, Tokyo 173-0003, Japan


The triethylamine salts of AcNHCH2CH2PO4H→6Manα(1→2)Manα1→OCH2CH2CH3 and AcNHCH2CH2PO4H→6Manα(1→2)Manα (1→6)Manα1→OCH2CH2CH3 were synthesized. These mannosyl residues were constructed by the dimethylphosphinothioate method. The introduction of the phosphodiester function was achieved by the hydrogen-phosphate method.

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Note | Special issue | Vol 52, No. 2, 2000, pp. 929 - 934
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DOI: 10.3987/COM-99-S71
Synthesis of New Chiral Amines, 2,6-Dimethyl-9-azabicyclo[3.3.1]nonane and Its Derivatives

Yasumasa Hamada,* Naoki Okamoto, and Osamu Hara

*Faculty of Pharmaceutical Sciences, Chiba University, 1-33 Yayoi-cho, Inage-ku, Chiba 263-8522, Japan


New chiral amines, 2,6-dimethyl-9-azabicyclo[3.3.1]nonane and its derivatives, were prepared starting from commercially available 1,5-dimethyl-1,5-cyclooctadiene followed by substitution reaction of the intermediate ditosylate with p-toluenesulfonamide under phase transfer conditions in 4 steps.

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Note | Special issue | Vol 52, No. 2, 2000, pp. 935 - 938
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DOI: 10.3987/COM-99-S80
Regioselective Hydroformylation of Citronellene Using a Novel Rhodium-Catalyst

Manfred T. Reetz,* Siegfried R. Waldvogel, and Richard Goddard

*Max-Planck-Institut für Kohlenforschung, Kaiser-Wilhelm-Platz 1, D-45470 Mülheim/Ruhr, Germany


The bidentate diphosphine N,N-bis-(P-(phosphabicyclo[3.3.1]-nonan)-methyl)-aniline is readily prepared by phosphanomethylation of aniline. It forms a Rh-complex which is a highly regioselective catalyst in the hydroformylation of citronellene.

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Note | Special issue | Vol 52, No. 2, 2000, pp. 939 - 944
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DOI: 10.3987/COM-99-S104
A Synthesis of 2,6-Bis(4R-hydroxymethyloxazolyl)pyridine as a Water Soluble Ligand

Seiji Iwasa,* Hideyuki Nakamura, and Hisao Nishiyama

*Toyohashi University of Technology, School of Materials Science, Tempaku-cho, Toyohashi, Aichi, 441-8580, Japan


C2 Symmetric 2,6-bis(oxazolyl)pyridine bearing hydroxymethyl group on the oxazoline rings was synthesized from L-serine methyl ester hydrochloride and pyridine-2,6-dicarboxylic acid in four steps (54 % overall yield).

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Review | Special issue | Vol 52, No. 2, 2000, pp. 945 - 976
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DOI: 10.3987/REV-99-SR3
Molecular Recognition of Pet Fluoroionophores

Kanji Kubo* and Tadamitsu Sakurai

*Institute of Advanced Material Study, 86 Kyushu University, Kasuga-koen, Kasuga, Fukuoka 816-8580, Japan


Recent advances in molecular recognitions of PET fluoroionophores are described.

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Review | Special issue | Vol 52, No. 2, 2000, pp. 977 - 1000
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DOI: 10.3987/REV-99-SR4
Carbazole-1,4-diones: Syntheses and Properties

Zouhair Bouaziz, Pascal Nebois, Ambroise Poumaroux, and Houda Fillion*

*Laboratoire de Chimie Organique, Institut des Sciences Pharmaceutiques et Biologiques, Université Claude Bernard, Lyon I, 8 avenue Rockfeller, 69373 Lyon Cedex 08, France


The synthetic approaches to carbazole-1,4-diones are described. Their synthetic usefulness in hetero Diels-Alder reactions towards azadienes, their behavior as precursors for carbazole-4,5-diones as well as their biological properties are reported.

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56 data found. 31 - 56 listedFirst Previous