YAMAGIWA Yoshiro

    Department of Science Associate Professor
Last Updated :2024/03/24

Researcher Information

Degree

  • Ph. D(Osaka City University)

J-Global ID

Research Interests

  • 有機合成 天然物 生物活性 ラジカルスカベンジャー 抗HIV   anti-HIV   Radical scavenger   Natural product   Organic synthesis   

Research Areas

  • Life sciences / Bioorganic chemistry
  • Nanotechnology/Materials / Structural/physical organic chemistry

Education

  •        - 1983  Osaka City University  理学研究科  化学
  •        - 1983  Osaka City University  Graduate School, Division of Natural Science
  •        - 1981  Osaka City University  Faculty of Science  化学
  •        - 1981  Osaka City University  Faculty of Science

Association Memberships

  • 有機合成化学協会   日本化学会   The Society of Synthetic Organic Chemistry, Japan   Chemical Society of Japan   

Published Papers

  • Yoshiro Yamagiwa; Nozomi Haruna; Hideki Kawakami; Kouichi Matsumoto
    Bulletin of the Chemical Society of Japan The Chemical Society of Japan 93 (8) 1036 - 1042 0009-2673 2020/08 [Refereed]
  • Noriyoshi Masuoka; Ken-ichi Nihei; Ayami Maeta; Yoshiro Yamagiwa; Isao Kubo
    FOOD CHEMISTRY ELSEVIER SCI LTD 166 270 - 274 0308-8146 2015/01 [Refereed]
     
    5-Pentadecatrienylresorcinol, isolated from cashew nuts and commonly known as cardol (C-15:3), prevented the generation of superoxide radicals catalysed by xanthine oxidase without the inhibition of uric acid formation. The inhibition kinetics did not follow the Michelis-Menten equation, but instead followed the Hill equation. Cardol (C-10:0) also inhibited superoxide anion generation, but resorcinol and cardol (C-5:0) did not inhibit superoxide anion generation. The related compounds 3,5-dihydroxyphenyl alkanoates and alkyl 2,4-dihydroxybenzoates, had more than a C9 chain, cooperatively inhibited but alkyl 3,5-dihydroxybenzoates, regardless of their alkyl chain length, did not inhibit the superoxide anion generation. These results suggested that specific inhibitors for superoxide anion generation catalysed by xanthine oxidase consisted of an electron-rich resorcinol group and an alkyl chain having longer than C9 chain. (C) 2014 Elsevier Ltd. All rights reserved.
  • K Nihei; Y Yamagiwa; T Kamikawa; Kubo, I
    BIOORGANIC & MEDICINAL CHEMISTRY LETTERS PERGAMON-ELSEVIER SCIENCE LTD 14 (3) 681 - 683 0960-894X 2004/02 [Refereed]
     
    Chamaecin (2-hydroxy-4-isopropylbenzaldehyde) was synthesized and tested for its tyrosinase inhibitory activity. It partially inhibits the oxidation Of L-3,4-dihydroxyphenylalanine (L-DOPA) catalyzed by mushroom tyrosinase with an IC50 of 2.3 muM. The inhibition kinetics analyzed by Dixon plots found that chamaecin is a mixed type inhibitor. This inhibition may come in part from its ability to form a Schiff base with a primary amino group in the enzyme. (C) 2003 Elsevier Ltd. All rights reserved.
  • Kubo, I; P Xiao; K Nihei; K Fujita; Y Yamagiwa; T Kamikawa
    JOURNAL OF AGRICULTURAL AND FOOD CHEMISTRY AMER CHEMICAL SOC 50 (14) 3992 - 3998 0021-8561 2002/07 [Refereed]
     
    In a rational approach to the design of antifungal agents against Saccharomyces cerevisiae, a series of alkyl gallates (3,4,5-trihydroxybenzoates) were synthesized and assayed. Nonyl gallate (1) was found to be the most effective with a minimum fungicidal concentration (MFC) of 12.5 mug/mL (42 muM), followed by octyl gallate (2) With an MFC of 25 mug/mL (89 muM). These MFCs are little influenced by pH values. A time-kill curve study indicates that nonyl gallate exhibits fungicidal activity against S. cerevisiae, at any growing stage. The antifungal activity of nonyl gallate is due primarily to its ability to act as a nonionic surface-active agent (surfactant). The length of the alkyl group is not a major contributor but plays a role in eliciting the activity to a large extent, As far as alkyl gallates are concerned, their antimicrobial spectra and potency depend largely on the hydrophobic portion of the molecules.
  • Kamikawa Tadao; Yamagiwa Yoshiro; Emoto Takahiro; Kubosaki Nobuo
    Symposium on the Chemistry of Natural Products, symposium papers Symposium on the chemistry of natural products (42) 697 - 702 2000/10 
    Naturally occurring phenazines have attracted considerable attention because of their interesting biological activities. One of the most promising methods for synthesizing polysubstituted phenazines developed by Holliman and co-workers was the reductive cyclization of o-nitrodiphenylamines (Method C). However, the yield was poor when competitive cyclization occurred. Recently, N-arylation has become more accessible owing to the advent of a new methodology developed by Hartwig and Buchwald. Here, we report on the use of the new method to synthesize phenazines using sequential palladium-mediated aniline arylation. Our method is based on the regiospecific bromination of o-nitrodiphenylamine 3, which is obtained from o-bromonitrobenzene 1 and aniline 2 by aniline arylation, to give bromide 4 (Method A), which is also obtained from 1 and o-bromoaniline 5 (Method B). Subsequent chemoselective reduction of the nitro group on 4 followed by the Hartwig-Buchwald aniline arylation affords the target phenazine. For the total synthesis of benthocyanin A, a powerful radical scavenger from the mycelium of Streptomyces prunicolor, and of phenazostatin A, a new neuronal cell protecting substances from the culture broth of Streptomyces sp. 833, we adapted the new methods to construct phenazines.
  • T Emoto; N Kubosaki; Y Yamagiwa; T Kamikawa
    TETRAHEDRON LETTERS PERGAMON-ELSEVIER SCIENCE LTD 41 (3) 355 - 358 0040-4039 2000/01 
    Phenazines were prepared by the palladium(II)-catalyzed intramolecular amination of aryl bromides 8, which were prepared with o-bromonitrobenzenes 3 and anilines 4 or 3 and o-bromoanilines 5 using palladium(II)-catalyzed aniline arylation. (C) 2000 Elsevier Science Ltd. All rights reserved.
  • Isao Kubo; Ikuyo Kinst-Hori; Yumi Kubo; Yoshiro Yamagiwa; Tadao Kamikawa; Hiroyuki Haraguchi
    Journal of Agricultural and Food Chemistry 48 (4) 1393 - 1399 0021-8561 2000 
    Tyrosinase inhibitory and antioxidant activity of gallic acid and its series of alkyl chain esters were investigated. All inhibited the oxidation of L-3,4-dihydroxyphenylalanine (L-DOPA) catalyzed by mushroom tyrosinase. However, gallic acid and its short alkyl chain esters were oxidized as substrates yielding the colored oxidation products. In contrast, the long alkyl chain esters inhibited the enzyme activity without being oxidized. This indicates that the carbon chain length is associated with their tyrosinase inhibitory activity, presumably by interacting with the hydrophobic protein pocket in the enzyme. On the other hand, the esters, regardless their carbon chain length, showed potent scavenging activity on the autoxidation of linoleic acid and 1,1-diphenyl-2-p-picryhydrazyl (DPPH) radical, suggesting that the alkyl chain length is not related to the activity. The effects of side-chain length of gallates in relation to their antibrowning activity are studied.
  • LP Wu; Y Yamagiwa; Ino, I; K Sugimoto; T Kuroda-Sowa; T Kamikawa; M Munakata
    POLYHEDRON PERGAMON-ELSEVIER SCIENCE LTD 18 (15) 2047 - 2053 0277-5387 1999 
    Copper(II) and iron(II, III) complexes of the tripodal ligand, tris(1-methyl-1H-imidazol-2-yl)methanol (Htmim), have been synthesized and characterized by elemental analysis, H-1 NMR and IR spectroscopies, magnetic moment measurement and X-ray crystallography. The structure of the copper complex, [Cu-4(tmim)(4)(CF3SO3)(2)](CF3SO3)(2). 2MeOH (1), can be regarded as a polyimidazole-linked tetranuclear cluster where each copper atom adopts a five-coordinate square-pyramidal geometry ligated by the tmim anion. The two iron complexes, [Fe-II(Htmim)(2)][(FeCl4)-Cl-II]. 4MeOH (2) and [Fe-III(Htmim)(2)][(FeCl4)-Cl-III](2)Cl (3), contain the isostructural [Fe(Htmim)(2)] cation and tetrahedral [FeCl4](-) anion. While Htmim shows a normal tripodal tridentate mode in the iron complexes capping one face of an essentially octahedral coordination sphere, its deprotonated species exhibit an unusual non-tripodal tetradentate coordination with copper(II) ions. The observed magnetic moment at room temperature for 1 is 1.13 BM per Cu atom, consistent with antiferromagnetic coupling between the copper(II) atoms of the tetramer. Both 2 and 3 show magnetic properties consistent with low-spin electronic configurations of the cation and high-spin nature of the metal ion in the anion. (C) 1999 Elsevier Science Ltd. All rights reserved.
  • LP Wu; Y Yamagiwa; T KurodaSowa; T Kamikawa; M Munakata
    INORGANICA CHIMICA ACTA ELSEVIER SCIENCE SA LAUSANNE 256 (1) 155 - 159 0020-1693 1997/03 
    The synthesis and characterization of the copper(II) complex [Cu(bim)(2.5)](ClO4)(2) . 2MeOH, where bim = 1,2-bis(imidazol-1'-yl) ethane, is described. The complex crystallizes in the monoclinic system, space group P2(1)/a, with cell constants a = 12.280(8), b = 12.533(5), c = 19.490(9) Angstrom, beta = 92.17(5)degrees and Z = 4. The structure was solved by a direct method and refined by full-matrix least squares to a residual R value of 0.064 and R-w of 0.066. The complex contains non-interacting ClO4- anions and a {[Cu(bim)(2.5)](2+)}(infinity) macrocation in which each metal ion involves a distorted square-based pyramidal coordination environment comprising five N atoms from five separate bim molecules. The total structure consists of two alternately stacked 2D sheets of copper(II) ions bridged through the bidentate imidazole molecules constituting a three-dimensional network. Consistent with the observed structural data the complex shows a typical axially symmetric ESR signal at room temperature.
  • Y Yamagiwa; Y Koreishi; S Kiyozumi; M Kobayashi; T Kamikawa; M Tsukino; H Goi; M Yamamoto; M Munakata
    BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN CHEMICAL SOC JAPAN 69 (11) 3317 - 3323 0009-2673 1996/11 
    1,5-Di(imidazol-1-yl)-3-[2-(imidazol-1-yl,7-di(imidazol-1-yl)-4-[3-(imidazol-1-yl)propyl]heptane, N,N',N ''-tris[2-(imidazol-4-yl)ethyl]benzene-1,3 and 1,3,5-tris[3-(imidazol-1-yl)propyl]benzene (TIPB) have been synthesized for a study of the formation and characteristics of zinc complexes. TIPB forms a crystalline zinc complex, not a tetrahedral complex but an octahedral complex. Other ligands form either microcrystalline complexes or polymer complexes with zinc.
  • T Kamikawa; Y Hanaoka; S Fujie; K Saito; Y Yamagiwa; K Fukuhara; Kubo, I
    BIOORGANIC & MEDICINAL CHEMISTRY PERGAMON-ELSEVIER SCIENCE LTD 4 (8) 1317 - 1320 0968-0896 1996/08 
    Three pyranoquinolone alkaloids isolated from two East African Fagara plants have been found to exhibit SRS-A antagonist action. Their synthesis has been accomplished, using a modified Coppola's method or a thermal cyclization followed by an electrocyclic ring closure. Copyright (C) 1996 Elsevier Science Ltd
  • T HIRAKI; Y YAMAGIWA; T KAMIKAWA
    TETRAHEDRON LETTERS PERGAMON-ELSEVIER SCIENCE LTD 36 (27) 4841 - 4844 0040-4039 1995/07 
    The straight-chain analog of penaresidins, azetidine alkaloids from the Okinawan marine sponge Penares sp., have been synthesized from D-xylose. The key step in the synthesis includes the biomimetic-type ring closure of phytosphingosines. The novel isomerization through an azabicylobutyl ion-pair is also described.
  • Nakashima H.; Hiraki T.; Yamagiwa Y.; Kamikawa T.
    Symposium on the Chemistry of Natural Products, symposium papers Symposium on the chemistry of natural products (36) 752 - 759 1994/09 
    We have studied the syntheses of bioactive lipids using natural chiral sources as starting materials. Hayashi et al. isolated a new ceramide digalactoside 1 as a main glycosphingolipid from the marine sponge Halichondria japonica. Penaresidin A 2 and B 3 were isolated as potent actomyosin ATPase activators from Okinawan marine sponge Penares sp. by Kobayashi et al. Here we describe synthetic studies of the ceramide part of I and the straight chain analog of 2. Synthesis of the ceramide part of 1. A partially protected ceramide part 20 of cerebroside 1 has been synthesized from L-ascorbic acid, and its absolute stereochemistry has been determined. The key step in the synthesis include the regioselective ring opening of chiral epoxide 7 with 2-alkyl-2-lithio-1,3-dithiane and the introduction of hydroxymethylene synthon using Dondoni's protocol to assemble C(1) and C(2) functionality. Synthesis of the straight chain analog of 2. The strategy for the construction of azetidine skeleton was a biogenetic-like intramolecular cyclization of a phytosphingosine analog 26, which, in turn, derived from xylose.
  • Hideki Nakashima; Norihiko Hirata; Takeru Iwamura; Yoshiro Yamagiwa; Tadao Kamikawa
    Journal of the Chemical Society, Perkin Transactions 1 2849 - 2857 1470-4358 1994 
    (2S,3S,4R)-2-[(2′R)-2-Benzoyloxydocosanoylamino]-16-methylheptadecane-1,3,4-triol 3,4-dibenzoate 32, a partially protected ceramide part of a cerebroside from the marine sponge Halichondria japonica, has been synthesized from L-ascorbic acid, and its absolute stereochemistry has been determined. The key steps in the synthesis include the regioselective ring opening of chiral epoxide 5 with a 2-alkyl-2-lithio-1,3-dithiane and the introduction of a hydroxymethylene synthon using Dondoni's protocol to assemble C(1) and C(2) functionality. © 1994 by the Royal Society of Chemistry. All Rights Reserved.
  • T KAMIKAWA; K NOGAWA; Y YAMAGIWA
    GLYCOCONJUGATE JOURNAL CHAPMAN HALL LTD 10 (3) 235 - 239 0282-0080 1993/06 
    2,3-Di-O-phytanyl-1-O-glucopyranosylglycerol and polar derivatives of its 6'-glucose moiety have been synthesized. The target molecule contains the diphytanyl-sn-glycerol moiety which is alpha-linked to glucose. The key step in its synthesis involves the coupling of phytanyl bromide and isopropylidene threitol. We also demonstrated that the 6'-hydroxyl group of glycolipids can be functionalized without protection of the sugar moiety.
  • Isao Kubo; Hisae Muroi; Masaki Himejima; Yoshiro Yamagiwa; Hiroyuki Mera; Kimihiro Tokushima; Shigeo Ohta; Tadao Kamikawa
    Journal of Agricultural and Food Chemistry 41 (6) 1016 - 1019 1520-5118 1993 
    A series of anacardic acids possessing different side-chain lengths were synthesized, and their antimicrobial activity was tested. In the case against Staphylococcus aureus, the anacardic acid having the C10 alkyl side chain was most active, while against Propionibacterium acnes, Streptococcus mutans, and Brevibacterium ammoniagenes, the anacardic acid possessing the C12 alkyl side chain was most effective. © 1993, American Chemical Society. All rights reserved.
  • PC VIEIRA; KUBO, I; H KUJIME; Y YAMAGIWA; T KAMIKAWA
    JOURNAL OF NATURAL PRODUCTS AMER SOC PHARMACOGNOSY 55 (8) 1112 - 1117 0163-3864 1992/08 
    Two novel acridone alkaloids, cuspanine [1] and cusculine [2], were isolated from the CH2Cl2 extract of the leaves of Angostura paniculata (Rutaceae). Their structures were established as 1-hydroxy-2,3,5,6-tetramethoxy-9-acridone for 1 and 1,2,3,5,6-pentamethoxy-9-acridone for 2 by means of spectroscopic studies, in particular nmr. These structural assignments were confirmed by synthesis, using a direct metallation method as a key reaction. Both alkaloids exhibited moderate molluscicidal activity against an aquatic snail, Biomphalaria glabrata, and cytotoxicity against several types of carcinoma cell lines.
  • Norihiko Hirata; Yoshiro Yamagiwa; Tadao Kamikawa
    Journal of the Chemical Society, Perkin Transactions 1 (9) 2279 - 2280 1470-4358 1991 
    The highly efficient stereoselective synthesis of D-erythro-C< inf> 18< /inf> -sphingosine from 3,4,6-tribenzyl- oxygalactal via 4,6-tribenzyloxy-5-hydroxyhexenal is described. © 1991 by the Royal Society of Chemistry.
  • KUBO, I; M OCHI; K SHIBATA; FJ HANKE; T NAKATSU; KS TAN; M TANIGUCHI; T KAMIKAWA; Y YAMAGIWA; M ARIZUKA; WF WOOD
    JOURNAL OF NATURAL PRODUCTS AMER SOC PHARMACOGNOSY 53 (1) 50 - 56 0163-3864 1990/01 
    The dibromocatechol α-O-methyllanosol [1], a methyl ether of lanosol, was isolated from both the MeOH and the CH 2 C1 2 extracts of Odonthalia washingtoniensis and Odonthalia floccosa. Its structure was confirmed through spectroscopic methods and through its synthesis. An investigation of its biological activities revealed that it exhibits a stimulating effect on the growth and elongation of certain terrestrial plants both in the in vivo and the in vitro systems. © 1990, American Chemical Society. All rights reserved.
  • Tetsuo Nakatsu; Timothy Johns; Isao Kubo; Katharine Milton; Masami Sakai; Katsuhiro Chatani; Ken Satto; Yoshiro Yamagiwa; Tadao Kamikawa
    Journal of Natural Products 53 (6) 1508 - 1513 1520-6025 1990 
    Two new biocidal quinolinone alkaloids, 3-methoxy-1-methyl-2-propyl-4-quinolone [1] and 2(1ʹ-ethylpropyl)-1-methyl-4-quinolone [2], were efficiently isolated using reversed-phase recycling hplc from the leaves of Esenbeckia leiocarpa. The structures were determined through spectroscopic data and confirmed by total synthesis. These alkaloids have antifeedant activities against the pink boll worm, Pectinophora gossypiella. © 1990, American Chemical Society. All rights reserved.
  • Kazuyuki Yamagata; Yoshiro Yamagiwa; Tadao Kamikawa
    Journal of the Chemical Society, Perkin Transactions 1 (12) 3355 - 3357 1470-4358 1990 
    Nucleophilic ring opening of chiral epoxy diols, derived from L-ascorbic acid, with 2-lithio-1,3-dithianes allowed preparation of long-chain (R)- and (S)-α-hydroxy acids of high optical purity. © 1990 by The Royal Society of Chemistry.
  • Hideo Iio; Kaoru Fujimori; Yoshiro Yamagiwa; Mitsugu Monden; Takashi Tokoroyama
    Journal of the Chemical Society, Perkin Transactions 1 1359 - 1360 1472-7781 1989/12 
    The title cis- and trans-clerodanes the structures of which correspond to that proposed for cascarillone have been efficiently synthesized from previously reported intermediates; neither proved to be identical with cascarillone.
  • K OHASHI; S KOSAI; M ARIZUKA; T WATANABE; Y YAMAGIWA; T KAMIKAWA; M KATES
    TETRAHEDRON PERGAMON-ELSEVIER SCIENCE LTD 45 (9) 2557 - 2570 0040-4020 1989 
    D-Erythro-1-deoxydihydroceramide-1-sulfonic acid, isolated from alkali-stable hydrogenated lipids in a non-photosynthetic marine diatom, Nitzschia alba, and (2S,3R)-N-palmitoyl-1-O-[6'-O-2-(N-methylamino)ethylphosphonyl-β-D-galacto-pyranosyl]-D-sphingosine, found in marine snail Turbo cornutus were synthesized via a common precursor (10) starting from galactose. © 1989.
  • Ohashi Kinji; Yamagiwa Yoshiro; Kamikawa Tadao
    International Symposium on the Chemistry of Natural Products Symposium on the chemistry of natural products 1988 316 - 316 1988/05
  • K OHASHI; Y YAMAGIWA; T KAMIKAWA; M KATES
    TETRAHEDRON LETTERS PERGAMON-ELSEVIER SCIENCE LTD 29 (10) 1185 - 1188 0040-4039 1988 [Refereed]
  • K OHASHI; S KOSAI; M ARIZUKA; T WATANABE; M FUKUNAGA; K MONDEN; T UCHIKODA; Y YAMAGIWA; T KAMIKAWA
    TETRAHEDRON LETTERS PERGAMON-ELSEVIER SCIENCE LTD 29 (10) 1189 - 1192 0040-4039 1988 
    The phosphonosphingoglycolipid (1) found in marine snail Turbo cornutus is synthesized from galactose as a chiral precursor via condensation of cerebroside (7) with protected phosphonic acid using DEC as the key step. © 1988.
  • Tadao Kamikawa; Satoru Fujie; Yoshiro Yamagiwa; Mujo Kim; Hitoshi Kawaguchi
    Journal of the Chemical Society, Chemical Communications (3) 195 - 196 0022-4936 1988 
    Clitocine, a new insecticidal nucleoside from the mushroom Clitocybe inversa, was synthesized.
  • T TOKOROYAMA; K FUJIMORI; T SHIMIZU; Y YAMAGIWA; M MONDEN; H IIO
    TETRAHEDRON PERGAMON-ELSEVIER SCIENCE LTD 44 (21) 6607 - 6622 0040-4020 1988 
    Title full: A general method for the synthesis of clerodane diterpenoids. Stereospecific total syntheses of (±)-15, 16-epoxy-cis-cleroda-3, 13(16), 14-triene and (±)-maingayic acid 1 1 Part 22 in Synthetic Studies on Terpenic Compounds. For Part 21 see: A. Kondo, T. Ochi, H. Iio, T. Tokoroyama and M. Siro, Chemistry Lett., 1987, 1491. Ref. 2 counts as Part 18. 2 2 A preliminary report of this work has been published: T. Tokoroyama, K. Fujimori, T. Shimizu, Y. Yamagiwa and H. Iio, J. Chem. Soc., Chem. Commun., 1983, 1516. A general method for the syntheses of cis- and trans-clerodane diterpenoids has been developed and its applications to the total syntheses of both representatives 11 and maingayic acid (32) in racemic forms are described. The common Δ 4 -3-octalone intermediates 2a and 2b were prepared from 3,4-dimethyl-2-cyclohexenone by a stereospecific conjugate addition-alkylation sequence and the subsequent thermodynamically controlled annelation. The dimethylcuprate addition to 2a followed by enolate trapping afforded stereospecifically the cis-alcohol 12, from which (±)-11 has been synthesized. On the other hand hydrocyanation of 2b gave trans-intermediate 33, and then it has been converted to (±)-maingayic acid (32). © 1988.
  • Y YAMAGIWA; K OHASHI; Y SAKAMOTO; S HIRAKAWA; T KAMIKAWA
    TETRAHEDRON PERGAMON-ELSEVIER SCIENCE LTD 43 (15) 3387 - 3394 0040-4020 1987 
    Syntheses of two anacardic acids [6-pentadecyl- and 6-(10-pentadecenyl) salicylic acid], inhibitors of prostaglandin synthetase and of the growth of certain insects, and ginkgoic acid via directive metallation is reported. © 1987.
  • KUBO, I; M KIM; GANJIAN, I; T KAMIKAWA; Y YAMAGIWA
    TETRAHEDRON PERGAMON-ELSEVIER SCIENCE LTD 43 (12) 2653 - 2660 0040-4020 1987 
    The isolation, characterization and an efficient synthesis of maesanin 1, a host defense stimulant isolated from an African medicinal plant Maesa lanceolata, is reported. © 1987.
  • Y FURUKAWA; Y YAMAGIWA; T KAMIKAWA
    JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS ROYAL SOC CHEMISTRY (16) 1234 - 1235 0022-4936 1986/08 
    3-(ω-Phenylalkyl)catechols were synthesized via directed metallation. © Royal Society of Chemistry.
  • K UCHINO; Y YAMAGIWA; T KAMIKAWA; KUBO, I
    TETRAHEDRON LETTERS PERGAMON-ELSEVIER SCIENCE LTD 26 (10) 1319 - 1320 0040-4039 1985 
    Racemic and optically active hepialone, a new sex-pheromonal component produced by the male moth, Hepialus californicus Bvd., was synthesized and thus confirmed the structure of the pheromone as (2R)-2,3-dihydro-2-ethyl-6-methyl-4H-pyran-4-one (1). © 1985.
  • Tokoroyama T.; Shimizu T.; Yamagiwa Y.; Monden M.; Iio H.
    Symposium on the Chemistry of Natural Products, symposium papers Symposium on the chemistry of natural products (26) 359 - 366 1983/09 
    In a continuation of our synthetic studies on clerodane diterpenoids, we have developed a general and versatile method for their syntheses. Its utility is demonstrated by the total syntheses of both cis and trans clerodane diterpenes, and by the contribution to the structure of cascarillone, a constituent of Cascarille oil. 1. Basic Strategy. The basic strategy rests on the conjugate addition of one carbon synthons to Δ^4-octal-3-one derivatives 2, which would afford cis or trans clerodane skeleton by appropriate choice of the reagents and conditions. (Scheme 1) 2. Synthesis of 15,16-Epoxy-cis-cleroda-3,13(16),14-triene 5. Conjugate addition of Me_2CuLi to octalone derivative 2a followed by trapping of the resulting enolate with HCHO gave a hydroxyketone 6, which was converted to the title natural product 5 by seven steps. (Scheme 2) 3. Syntheses of Maingayic Acid 19 and Annonene 20. Hydrocyanation of octalone intermediate 2b with Et_2AlCN gave stereospecifically a trans product 21, from which the total synthesis of maingayic acid, a piscicidal plant constituent, was accomplished by eleven steps via an aldehyde 33. Since 33 has been converted to annonene 20, our work constitutes also the formal synthesis of 20. (Scheme 3) 4. Structure Studies of Cascarillone. A cis-clerodane structure 34 was assigned to cascarillone solely on the basis of spectroscopic speculation. Our synthetic product 41 prepared starting from 7 has turned out to be not identical with cascarillone. Therefore the trans structure 42 is more likely for it and the confirmation of this proposal by synthesis is on progress.
  • T TOKOROYAMA; K FUJIMORI; T SHIMIZU; Y YAMAGIWA; M MONDEN; H IIO
    JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS ROYAL SOC CHEMISTRY (24) 1516 - 1518 0022-4936 1983 
    Application of stereospecific conjugate addition reactions to Δ 4 -3-octalone intermediates has led to the total synthesis of both cis- and trans-clerodane diterpenes.

Books etc

Conference Activities & Talks

  • (2PB-61)Synthetic studies of Cytonic Acids A and B  [Not invited]
    YAMASHITA Taiki; YAMAGIWA Yoshiro; NAKAGAWA Takayo
    日本化学会第97春期年会  2017/03
  • (3PB-223)Synthetic study of Integrastatins  [Not invited]
    KAWAKAMI Hideki; SHIGEKAWA Yoya; YAMAGIWA Yoshiro
    日本化学会第96春期年会  2016/03
  • (3PB-222)Total Synthesis of Integracins A and B  [Not invited]
    Fujita Atsushi; TAKAYAMA Yoshiko; MAEKAWA Takehiko; YAMAGIWA Yoshiro
    日本化学会第96春期年会  2016/03
  • 岡島史典; 樋口琢磨; 山際由朗
    日本化学会講演予稿集  2010/03  東大阪  日本化学会台90春期年会
     
    放線菌Streptomyces prunicolorより単離された Benthocyanin Aは、高度に共役したフロフェナジン骨格と ゲラニル側鎖を持ち、ラジカルスカベンジャーとしての活 性を有することが報告されている。我々が報告したHartwig-Buchwald法によるフェナジン類の一般的合成法ではN-ゲラニル側鎖を有するフェナジン類の合成は困難だった。そこで、ジ ヒドロフェナジン環の一方のNHを保護した無水イサト酸型の中間体とNHの保護基を用いない Benthocyanin Aにより近い中間体を想定し、これらの合成を試みた。また、その際に遭遇した予期しない生成物につい ても報告した。
  • 山際由朗; 原孝徳; 矢田幸昌; 左近直樹
    日本化学会講演予稿集  2007/03
  • 山際由朗; 寺田勇介
    日本化学会講演予稿集  2006/03
  • 菱田智之; 山際由朗
    日本化学会講演予稿集  2004/03
  • 片岡慎太郎; 山田健; 山際由朗; 神川忠雄
    日本化学会講演予稿集  2003/03  日本化学会第83春季年会(東京)
     
    パラジウムを触媒としたSuzukiカップリング反応をキーステップとして、中央の芳香環に4つの酸素官能基を有するp.terphenylの効率的な合成法及びその誘導体kynapcin.12の全合成について検討を行った。
  • 中野恵望子; 佐々木幹子; 榎本聡; 山際由朗; 神川忠雄
    日本化学会講演予稿集  2002/03  日本化学会第 81 春季年会(東京)
     
    パラジウムを触媒としたアリルメシラートと芳香族亜鉛化合物との立体選択的カップリング反応をキーステップとして、 糸状菌の一種から単離された神経突起成長促進物質 Parvisporin の合成を試みた。
  • 酒井康行; 山際由朗; 神川忠雄
    日本化学会講演予稿集  2001/03  日本化学会 第 79 回春季年会 (神戸)
     
    Hartwig Buchwald 法を用いて、 分子間 arylamination、 ついで分子内 arylamination を行い、 フェナジン誘導体を合成する方法を開発した。 この方法を用いて、 神経細胞保護物質 Phenazostatin A の全合成を行った。
  • 榎本聡; 小林豊茂; 山際由朗; 神川忠雄
    日本化学会講演予稿集  2001/03  日本化学会 第 79 回春季年会 (神戸)
     
    アリールメシラートと芳香族亜鉛化合物を、 パラジウムを触媒としてカップリングさせると、 立体選択的にポリプレニルヒドロキノンが合成できることを見出した。 この反応を利用して、 クモヒトデから単離された、 ファルネシルヒドロキノン euplexide C を合成した。
  • 神川忠雄; 山際由朗; 榎本貴弘; 窪崎伸夫
    天然有機化合物討論会講演要旨集  2000/10
  • Kamikawa Tadao; Yamagiwa Yoshiro; Emoto Takahiro; Kubosaki Nobuo
    天然有機化合物討論会講演要旨集  2000/10 
    Naturally occurring phenazines have attracted considerable attention because of their interesting biological activities. One of the most promising methods for synthesizing polysubstituted phenazines developed by Holliman and co-workers was the reductive cyclization of o-nitrodiphenylamines (Method C). However, the yield was poor when competitive cyclization occurred. Recently, N-arylation has become more accessible owing to the advent of a new methodology developed by Hartwig and Buchwald. Here, we report on the use of the new method to synthesize phenazines using sequential palladium-mediated aniline arylation. Our method is based on the regiospecific bromination of o-nitrodiphenylamine 3, which is obtained from o-bromonitrobenzene 1 and aniline 2 by aniline arylation, to give bromide 4 (Method A), which is also obtained from 1 and o-bromoaniline 5 (Method B). Subsequent chemoselective reduction of the nitro group on 4 followed by the Hartwig-Buchwald aniline arylation affords the target phenazine. For the total synthesis of benthocyanin A, a powerful radical scavenger from the mycelium of Streptomyces prunicolor, and of phenazostatin A, a new neuronal cell protecting substances from the culture broth of Streptomyces sp. 833, we adapted the new methods to construct phenazines.
  • Nakashima H; Hiraki T; Yamagiwa Y; Kamikawa T
    天然有機化合物討論会講演要旨集  1994/09 
    We have studied the syntheses of bioactive lipids using natural chiral sources as starting materials. Hayashi et al. isolated a new ceramide digalactoside 1 as a main glycosphingolipid from the marine sponge Halichondria japonica. Penaresidin A 2 and B 3 were isolated as potent actomyosin ATPase activators from Okinawan marine sponge Penares sp. by Kobayashi et al. Here we describe synthetic studies of the ceramide part of I and the straight chain analog of 2. Synthesis of the ceramide part of 1. A partially protected ceramide part 20 of cerebroside 1 has been synthesized from L-ascorbic acid, and its absolute stereochemistry has been determined. The key step in the synthesis include the regioselective ring opening of chiral epoxide 7 with 2-alkyl-2-lithio-1,3-dithiane and the introduction of hydroxymethylene synthon using Dondoni's protocol to assemble C(1) and C(2) functionality. Synthesis of the straight chain analog of 2. The strategy for the construction of azetidine skeleton was a biogenetic-like intramolecular cyclization of a phytosphingosine analog 26, which, in turn, derived from xylose.
  • Tokoroyama T; Shimizu T; Yamagiwa Y; Monden M; Iio H
    天然有機化合物討論会講演要旨集  1983/09 
    In a continuation of our synthetic studies on clerodane diterpenoids, we have developed a general and versatile method for their syntheses. Its utility is demonstrated by the total syntheses of both cis and trans clerodane diterpenes, and by the contribution to the structure of cascarillone, a constituent of Cascarille oil. 1. Basic Strategy. The basic strategy rests on the conjugate addition of one carbon synthons to Δ^4-octal-3-one derivatives 2, which would afford cis or trans clerodane skeleton by appropriate choice of the reagents and conditions. (Scheme 1) 2. Synthesis of 15,16-Epoxy-cis-cleroda-3,13(16),14-triene 5. Conjugate addition of Me_2CuLi to octalone derivative 2a followed by trapping of the resulting enolate with HCHO gave a hydroxyketone 6, which was converted to the title natural product 5 by seven steps. (Scheme 2) 3. Syntheses of Maingayic Acid 19 and Annonene 20. Hydrocyanation of octalone intermediate 2b with Et_2AlCN gave stereospecifically a trans product 21, from which the total synthesis of maingayic acid, a piscicidal plant constituent, was accomplished by eleven steps via an aldehyde 33. Since 33 has been converted to annonene 20, our work constitutes also the formal synthesis of 20. (Scheme 3) 4. Structure Studies of Cascarillone. A cis-clerodane structure 34 was assigned to cascarillone solely on the basis of spectroscopic speculation. Our synthetic product 41 prepared starting from 7 has turned out to be not identical with cascarillone. Therefore the trans structure 42 is more likely for it and the confirmation of this proposal by synthesis is on progress.
  • Tokoroyama T; Shimizu T; Yamagiwa Y; Monden M; Iio H
    Symposium on the Chemistry of Natural Products, symposium papers  1983 
    In a continuation of our synthetic studies on clerodane diterpenoids, we have developed a general and versatile method for their syntheses. Its utility is demonstrated by the total syntheses of both cis and trans clerodane diterpenes, and by the contribution to the structure of cascarillone, a constituent of Cascarille oil. 1. Basic Strategy. The basic strategy rests on the conjugate addition of one carbon synthons to Δ^4-octal-3-one derivatives 2, which would afford cis or trans clerodane skeleton by appropriate choice of the reagents and conditions. (Scheme 1) 2. Synthesis of 15,16-Epoxy-cis-cleroda-3,13(16),14-triene 5. Conjugate addition of Me_2CuLi to octalone derivative 2a followed by trapping of the resulting enolate with HCHO gave a hydroxyketone 6, which was converted to the title natural product 5 by seven steps. (Scheme 2) 3. Syntheses of Maingayic Acid 19 and Annonene 20. Hydrocyanation of octalone intermediate 2b with Et_2AlCN gave stereospecifically a trans product 21, from which the total synthesis of maingayic acid, a piscicidal plant constituent, was accomplished by eleven steps via an aldehyde 33. Since 33 has been converted to annonene 20, our work constitutes also the formal synthesis of 20. (Scheme 3) 4. Structure Studies of Cascarillone. A cis-clerodane structure 34 was assigned to cascarillone solely on the basis of spectroscopic speculation. Our synthetic product 41 prepared starting from 7 has turned out to be not identical with cascarillone. Therefore the trans structure 42 is more likely for it and the confirmation of this proposal by synthesis is on progress.

MISC

Research Grants & Projects

  • Synthetic studies of the HIV integrase inhibitors
    Date (from‐to) : 2002
  • 日本学術振興会:科学研究費助成事業
    Date (from‐to) : 1991 -1991 
    Author : 神川 忠雄; 山際 由朗
     
    近年複合脂質が生物認識、細胞分化調節、細胞ー細胞間認識、情報の仲介、免疫反応等に深い関わりがあることが分かってきた。脳、神経等に存在するセラミドホスホコリン、海産動物の細胞膜を構成するスフィンゴ糖脂質の化学は、最近ようやくその全貌が明らかになりつつある。しかしながら、これらの複合脂質は複雑な混合物で、単離・同定が困難なために、単一の状態での研究例は非常に少ない。これらの化合物の化学的、物理的諸性質を解明するには純物質の合成が不可欠であって、本研究は複合脂質の効率的合成法の開発を目指して行われた。合成の標的化合物として、好ハロゲン菌の細胞膜成分、ジフィタニルエ-テルグリセロ糖脂質(a)、および海綿の細胞膜成分スフィンゴ糖脂質(b)を選び、平成3年度にはつぎのような成果を得た。 1.すでに我々が確立したdlーグリセロジフィタニルエ-テルの合成法を応用し、糖脂質を合成し、その糖のCー6位に種々の極性基を導入して、化合物(a)、および(c)の合成に成功した。この種の脂質は相転移温度が低いという興味ある性質を持っている。今後生物活性についても研究する予定である。 2.スフィンゴ糖脂質の重要構成成分であるスフィンゴシンをdーガラクト-スから効率よく合成する方法を開発した。この方法は、スフィンゴ型糖脂質の簡便な合成法として大いに利用価値があるものと思われる。また、アスコルビン酸からフィトスフィンゴシンを合成する方法を開発した。この成果は複合脂質の絶対配置を合成的に決定するの大きく貢献するものと思われる。これらの実績を踏まえて、さらに複合脂質(b)の全合成を目指している。
  • 日本学術振興会:科学研究費助成事業
    Date (from‐to) : 1990 -1990 
    Author : 山際 由朗
  • 日本学術振興会:科学研究費助成事業
    Date (from‐to) : 1989 -1989 
    Author : 神川 忠雄; 山際 由朗
     
    近年複合糖脂質が生体認識や細胞分化と深い関わりがあることが分かってきた。海産軟体動物の細胞膜を構成するスフィンゴ糖脂質の化学は最近ようやくその全貌が明らかにされつつあるところである。これらは複雑な組成を持つ混合物であり、その物理的ならびに化学的性質はいまだにほとんど分かっていないが、生体内での機能はやはり情報伝達、細胞分化、自他認識に関与していることが示唆されている。これらの諸性質の解明には純物質の合成が不可欠であるが、複合脂質の合成はいまだに解決されていない点が多く、本研究はスィンゴ糖脂質の効率よい合成法を開発するのが目的である。この研究は次の二つのプロシエクトから成り立っている。 1.サザエの筋肉および内臓部より単離されたホスホノセラミドトリへキソシド(1)の合成:ガラクト-スを出発物質に用いホスホノセラミドモノヘキソシドの全合成に成功し、Tetrahedronに投稿した。現在この方法を改良して(1)の全合成を検討中である。 2.ダイダイイソカイメンより単離されたセラミドジヘキソシド(2)の合成:(2R)-オキシカルボン酸をアルコルビン酸より立体選択的に合成することに成功した。またファイトスフィンゴシン部分もマンノ-ス、ガラクト-ス、アスコルビン酸をそれぞれ出発物質とする合成法を開発し、現在最終標的化合物への誘導を検討中である。これらの結果の一部は日本化学会第59春季年会において発表の予定である。
  • 抗HIV活性を有する化合物の合成
  • 抗酸化機能を有する天然物の合成
  • 生物活性天然有機化合物の合成
  • Synthesis of naturaly occuring radical scavengers
  • Synthesis of bio-active natural products


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