Researchers Database

Matsumoto Arimasa

    Faculty Division of Natural Sciences Research Group of Chemistry Assistant Professor
Last Updated :2021/08/06

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Degree

  • Ph. D, The University of Tokyo

Research Areas

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

Research Experience

  • 2016 - 2017, 東京理科大学理学部応用化学科 嘱託講師
  • 2016 - 2017, Tokyo University of Science, Lecturer
  • 2012 - 2016, 東京理科大学理学部応用化学科 嘱託助教
  • 2012 - 2016, Tokyo University of Science, Assistant Professor
  • 2009 - 2012, 日本学術振興会 特別研究院(DC1)
  • 2009 - 2012, Japan Society for the Promotion of Science, Research Fellowship for Young Scientists

Education

  • - 2012, The University of Tokyo, 理学系研究科, 化学専攻, Japan
  • - 2012, The University of Tokyo, Graduate School, Division of Science, Department of Chemistry
  • - 2009, The University of Tokyo, 理学系研究科, 化学専攻, Japan
  • - 2009, The University of Tokyo, Graduate School, Division of Science, Department of Chemistry
  • - 2007, The University of Tokyo, Faculty of Science, Department of Chemistry, Japan
  • - 2007, The University of Tokyo, Faculty of Science, Department of Chemistry

Awards

  • Springer Thesis Prize, 2014
  • 有機合成化学協会 研究企画賞, 2013, JPN
  • 25th International Synposium on Molecular Chirality (Chirality 2013:ISCD-25) Poster Award, 2013
  • 東京大学大学院理学系研究科 研究奨励賞, 2012, JPN
  • 万有生命科学振興国際交流財団 大津会議アワードフェロー, 2010, JPN

Published Papers

  • A Tetrakisquinoline Analog of Calcium Indicator Quin2 for Fluorescence Detection of Cd2+

    Yuji Mikata; Minori Kaneda; Marin Tanaka; Satoshi Iwatsuki; Hideo Konno; Arimasa Matsumoto

    © 2020 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim Quin2 (2-{2-[bis(carboxymethyl)amino-5-methylphenoxy]methyl}-6-methoxy-8-[bis(carboxymethyl)amino]quinoline) is a well-known fluorescent Ca2+ indicator. In this study, we replaced its four carboxy groups with quinolines and deleted a methyl group on the benzene ring to afford TQquin2 [N,N,N',N'-tetrakis(2-quinolylmethyl)-8-amino-2-(2-aminophenoxy)methyl-6-methoxyquinoline]. In methanol solution, TQquin2 exhibited fluorescence enhancement toward Cd2+ with excellent selectivity., 08 Mar. 2020, European Journal of Inorganic Chemistry, 2020 (9), 757 - 763, doi

    Scientific journal

  • Switching of Fluorescent Zn/Cd Selectivity in N, N, N′, N′-Tetrakis(6-methoxy-2-quinolylmethyl)-1,2-diphenylethylenediamine by One Asymmetric Carbon Atom Inversion

    Yuji Mikata; Kana Nozaki; Marin Tanaka; Hideo Konno; Arimasa Matsumoto; Masaya Kawamura; Shin Ichiro Sato

    © 2020 American Chemical Society. A quinoline-based hexadentate ligand, (S,S)-N,N,N′,N′-tetrakis(6-methoxy-2-quinolylmethyl)-1,2-diphenylethylenediamine ((S,S)-6-MeOTQPh2EN), exhibits fluorescence enhancement at 498 nm upon addition of 1 equiv of Zn2+ (IZn/I0 = 12, φZn = 0.047) in aqueous DMF solution (DMF/H2O = 2:1). Addition of 1 equiv of Cd2+ affords a much smaller fluorescence increase at the same wavelength (ICd/I0 = 2.5, ICd/IZn = 21%). The trivalent metal ions such as Al3+, Cr3+, and Fe3+ also exhibit fluorescence enhancement at 395 nm (IAl/I0 = 22, ICr/I0 = 6 and IFe3+/I0 = 13). In contrast, meso-6-MeOTQPh2EN exhibits a Cd2+-selective fluorescence increase at 405 nm in the presence of 1 equiv of metal ion (ICd/I0 = 11.5, φCd = 0.022), while Zn2+ induces a smaller fluorescent response under the same experimental conditions (IZn/I0 = 3.3, IZn/ICd = 29%). In this case, the fluorescence intensities of meso-6-MeOTQPh2EN in the presence of a large amount of Zn2+ and Cd2+ become similar. This diastereomer-dependent, fluorescent metal ion specificity is derived from the Zn2+-specific intramolecular excimer formation in (S,S)-6-MeOTQPh2EN-Zn2+ complex and higher binding affinity of meso-6-MeOTQPh2EN with Cd2+ in comparison to Zn2+. The more conformationally restricted diastereomeric pair, namely, cis- and trans-TQDACHs (cis- and trans-N,N,N′,N′-tetrakis(2-quinolylmethyl)-1,2-diaminocyclohexanes), both exhibit Zn2+-specific fluorescence enhancement because of the high metal binding affinity and intramolecular excimer forming property derived from the rigid DACH backbone., 12 Feb. 2020, Inorganic Chemistry, doi

    Scientific journal

  • Role of asymmetric autocatalysis in the elucidation of origins of homochirality of organic compounds

    Kenso Soai; Tsuneomi Kawasaki; Arimasa Matsumoto

    May 2019, SYMMETRY-BASEL, 11 (5), 694 - 694, doi

  • Formation of enantioenriched alkanol with stochastic distribution of enantiomers in the absolute asymmetric synthesis under heterogeneous solid_vapor phase conditions

    Yoshiyasu Kaimori; Yui Hiyoshi; Tsuneomi Kawasaki; Arimasa Matsumoto; Kenso Soai

    04 Apr. 2019, Chem. Commun., (55), 5223 - 5226, doi

  • Achiral amino acid glycine acts as an origin of homochirality in asymmetric autocatalysis

    Arimasa Matsumoto; Hanae Ozaki; Sumeru Tsuchiya; Toru Asahi; Meir Lahav; Tsuneomi Kawasaki; Kenso Soai

    01 Apr. 2019, Organic & Biomolecular Chemistry, (17), 4200 - 4203, doi

  • Methoxy-substituted tetrakisquinoline analogs of EGTA and BAPTA for fluorescence detection of Cd 2+

    Yuji Mikata; Minori Kaneda; Hideo Konno; Arimasa Matsumoto; Shin Ichiro Sato; Masaya Kawamura; Satoshi Iwatsuki

    © The Royal Society of Chemistry. EGTA (ethylene glycol bis(2-aminoethyl ether)-N,N,N′,N′-tetraacetic acid) and BAPTA (1,2-bis(2-aminophenoxy)ethane-N,N,N′,N′-tetraacetic acid) are well-known Ca 2+ chelators that have four carboxylates, two nitrogen atoms and two ether oxygen atoms. In the present study, we prepared EGTQ (N,N,N′,N′-tetrakis(2-quinolylmethyl)-1,2-bis(2-aminoethoxy)ethane) and BAPTQ (N,N,N′,N′-tetrakis(2-quinolylmethyl)-1,2-bis(2-aminophenoxy)ethane) as quinoline alternatives of EGTA and BAPTA, respectively. In methanol-HEPES buffer solution (9 : 1, 50 mM HEPES, 0.1 M KCl, pH = 7.5), EGTQ exhibits fluorescence enhancement induced by Zn 2+ and Cd 2+ with poor selectivity, but BAPTQ did not exhibit a fluorescence response to either metal ion. Introduction of three methoxy substituents at the 5,6,7-positions of each quinoline moiety in BAPTQ specifically enhanced the fluorescence intensity of the Cd 2+ complex, establishing the Cd 2+ -specific probe TriMeOBAPTQ (N,N,N′,N′-tetrakis(5,6,7-trimethoxy-2-quinolylmethyl)-1,2-bis(2-aminophenoxy)ethane). In contrast, TriMeOEGTQ (N,N,N′,N′-tetrakis(5,6,7-trimethoxy-2-quinolylmethyl)-1,2-bis(2-aminoethoxy)ethane) maintains a poor Cd 2+ /Zn 2+ selectivity in its fluorescence response. Although the crystal structures of Cd 2+ /Zn 2+ complexes with EGTQ and BAPTQ derivatives reveal the formation of multiple components including mononuclear and dinuclear complexes, the dinuclear Cd 2+ and Zn 2+ complexes with a linearly extended structure are regarded as possible fluorescent species in the solution. The conformational restriction of BAPTQ due to the orthophenylene moieties in the molecular skeleton is responsible for the formation of the weakly fluorescent, OH-bridged dizinc complex, which is critical to the strict Cd 2+ -specificity in the fluorescence response of TriMeOBAPTQ., 2019, Dalton Transactions, 48 (12), 3840 - 3852, doi;pubmed;scopus;scopus_citedby

    Scientific journal

  • Pyrophosphate-Induced Intramolecular Excimer Formation in Dinuclear Zinc(II) Complexes with Tetrakisquinoline Ligands

    Yuji Mikata; Risa Ohnishi; Risa Nishijima; Arimasa Matsumoto; Hideo Konno

    © 2018 American Chemical Society. Dinuclear Zn2+ complexes with HTQHPN (N,N,N′,N′-tetrakis(2-quinolylmethyl)-2-hydroxy-1,3-propanediamine) derivatives have been prepared, and their pyrophosphate (PPi, P2O74-) sensing properties were examined. The ligand library includes six HTQHPN derivatives with electron-donating/withdrawing substituents, an extended aromatic ring, and six-membered chelates upon zinc binding. Complexation of ligand with 2 equiv of Zn2+ promotes small to moderate fluorescence enhancement around 380 nm, but in the cases of HTQHPN, HT(6-FQ)HPN (N,N,N′,N′-tetrakis(6-fluoro-2-quinolylmethyl)-2-hydroxy-1,3-propanediamine), and HT(8Q)HPN (N,N,N′,N′-tetrakis(8-quinolylmethyl)-2-hydroxy-1,3-propanediamine), subsequent addition of PPi induced a significant fluorescence increase around 450 nm. This fluorescence enhancement in the long-wavelength region is attributed to the conformational change of the bis-(quinolylmethyl)amine moiety which promotes intramolecular excimer formation between adjacent quinolines upon binding with PPi. The structures of PPi- and phosphate-bound dizinc complexes were revealed by X-ray crystallography utilizing phenyl-substituted analogues. The zinc complex with HT(8Q)HPN exhibits the highest signal enhancement (IPPi/I0 = 12.5) and selectivity toward PPi sensing (IATP/IPPi = 20% and IADP/IPPi = 25%). The fluorescence enhancement turned to decrease gradually after the addition of more than 1 equiv of PPi due to the removal of zinc ion from the ligand-zinc-PPi ternary complex, allowing the accurate determination of PPi concentrations at the fluorescence maximum composition. The practical application of the present method was demonstrated monitoring the enzymatic activity of pyrophosphatase., 02 Jul. 2018, Inorganic Chemistry, 57 (13), 7724 - 7734, doi;pubmed;scopus;scopus_citedby

    Scientific journal

  • Carbohydrate-Appended TQNPEN [N,N,N′,N′-Tetrakis(2-quinolylmethyl)-3-aza-1,5-pentanediamine] Derivatives for Fluorescence Detection of Intracellular Cd2+

    Yuji Mikata; Kana Nozaki; Minori Kaneda; Keiko Yasuda; Masato Aoyama; Satoshi Tamotsu; Arimasa Matsumoto

    © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim Carbohydrate-appended TQNPEN [N,N,N′,N′-tetrakis(2-quinolylmethyl)-3-aza-1,5-pentanediamine] derivatives were developed as intracellular fluorescent Cd2+ sensors. Glucose (L1), galactose (L2), and maltose (L3) were utilized as sugar moieties. All glycosylated derivatives exhibit a fluorescence increase (ICd/I0 = 11–25) at 415 nm upon addition of 1 equiv. of Cd2+; however, 1 equiv. of Zn2+ induces negligible fluorescence change due to weak metal–ligand interaction (IZn/I0 = 3, IZn/ICd = 11–31 %). The properties of the Cd2+ complex with parent TQNPEN, including maximum fluorescence wavelength and lifetime, Cd2+ specificity of the fluorescence, and strong metal binding affinity, were well preserved in L1–L3. The intracellular Cd2+ detection was successfully achieved by glucose- and galactose-appended derivatives L1 and L2, likely due to enhanced cell membrane permeability and intracellular distribution in HeLa cells., 29 Jun. 2018, European Journal of Inorganic Chemistry, 2018 (24), 2755 - 2761, doi;scopus;scopus_citedby

    Scientific journal

  • Asymmetric autocatalysis of pyrimidyl alkanol and related compounds. Self-replication, amplification of chirality and implication for the origin of biological enantioenriched chirality

    Kenso Soai; Tsuneomi Kawasaki; Arimasa Matsumoto

    We discovered asymmetric autocatalysis in the enantioselective addition of diisopropylzinc to pyrimidine-5-carbaldehyde, where the product 5-pyrimidyl alkanol acts as a highly efficient asymmetric autocatalyst to afford more of itself (Soai reaction). Asymmetric autocatalysis proceeded quantitatively (> 99% yield), affording itself as a near enantiomerically pure (> 99.5% ee) product. An extremely low enantiomeric excess (ca. 0.00005% ee) can automultiply during three rounds of consecutive asymmetric autocatalysis to > 99.5% ee by asymmetric amplification. Circularly polarized light, and inorganic and organic crystals, act as the origin of chirality to trigger asymmetric autocatalysis. Asymmetric autocatalysis has enormous power to recognize and amplify the chirality of hydrogen, carbon, oxygen, and nitrogen isotopomers. Moreover, absolute asymmetric synthesis, i.e., the formation of enantioenriched compounds without the intervention of any chiral factor, is realized by asymmetric autocatalysis. By using designed molecules based on 5-pyrimidyl alkanol, the intramolecular asymmetric control, self-replication, and improvement of chiral multifunctionalized large molecules has been developed by applying asymmetric autocatalysis., Elsevier Ltd, 19 Apr. 2018, Tetrahedron, 74 (16), 1973 - 1990, doi

  • Reversal of the sense of enantioselectivity between 1-and 2-aza[6]helicenes used as chiral inducers of asymmetric autocatalysis

    Arimasa Matsumoto; Kento Yonemitsu; Hanae Ozaki; Jiri Misek; Ivo Stary; Irena G. Stara; Kenso Soai

    Reversal of the sense of enantioselectivity was observed between 1-aza[6]helicene 2 and 2-aza[6]helicene 3 employed as chiral inducers of asymmetric autocatalysis of pyrimidyl alkanol. In the presence of (P)-(+)-1-aza[6]helicene 2, the reaction of pyrimidine-5-carbaldehyde 1 with diisopropylzinc afforded, in conjunction with asymmetric autocatalysis, (S)-pyrimidyl alkanol 4 with high ee. Surprisingly, the reaction in the presence of (P)-(+)-2-aza[6]helicene 3 gave the opposite enantiomer of (R)-alkanol 4 with high ee. In the same manner, (M)-(-)-2 and (M)-(-)-3 afforded (R)-and (S)-alkanol 4, respectively. The sense of enantioselectivity is controlled not only by the helicity of the azahelicene derivatives but also by the position of the nitrogen atom., ROYAL SOC CHEMISTRY, Feb. 2017, ORGANIC & BIOMOLECULAR CHEMISTRY, 15 (6), 1321 - 1324, doi;web_of_science

    Scientific journal

  • Asymmetric Autocatalysis and the Origin of Homochirality

    Kenso Soai; Arimasa Matsumoto

    Asymmetric autocatalysis is a reaction in which chiral product acts as chiral catalyst for its own production. Pyrimdin-5-yl-iso-propylcarbinol (pyrimidyl alkanol) was found to be a highly efficient asymmetric autocatalyst in the enantioselective addition of diisopropyl zinc to pyrimidine-5-carbaldehyde to produce more of itself (Soai reaction). The process is the automultiplicaion, i.e., catalytic self-replication, of a chiral compound. Pyrimidyl alkanol with extremely low enantiomeric excess (ee) automultiplies and is amplified during three consecutive asymmetric autocatalyses to reach >99.5% ee. By using asymmetric autocatalysis, the origin of homochirality has been examined. Circularly polarized light, inorganic chiral crystals such as quartz, enantiotopic surface of achiral inorganic chiral such as gypsum, chiral crystals of achiral organic compounds, chiral compounds of isotope (hydrogen, carbon, oxygen, nitrogen) substitution, acting as chiral initiators in asymmetric autocatalysis, can be correlated to the highly enantioenriched products. Spontaneous absolute asymmetric synthesis was achieved without the intervention of any chiral factor., AMER CHEMICAL SOC, 2017, STEREOCHEMISTRY AND GLOBAL CONNECTIVITY: THE LEGACY OF ERNEST L ELIEL, VOL 2, 1258, 27 - 47, web_of_science

    International conference proceedings

  • Point-to-Point Ultra-Remote Asymmetric Control with Flexible Linker

    Tsuneomi Kawasaki; Yasuyuki Ishikawa; Yoshihiro Minato; Takashi Otsuka; Shigeru Yonekubo; Itaru Sato; Takanori Shibata; Arimasa Matsumoto; Kenso Soai

    An ultra-remote intramolecular (point-to-point) asymmetric control through 38 bonds (1,39-asymmetric induction) has been achieved by using the principle of direct supramolecular orientation of catalytic and reactive moieties in asymmetric autocatalysis. We found the highly stereoselective diisopropylzinc addition reaction using designed molecules possessing pyrimidine sites at each terminal of a conformationally flexible simple methylene chain., WILEY-V C H VERLAG GMBH, Jan. 2017, CHEMISTRY-A EUROPEAN JOURNAL, 23 (2), 282 - 285, doi;web_of_science

    Scientific journal

  • Achiral Inorganic Gypsum Acts as an Origin of Chirality through Its Enantiotopic Surface in Conjunction with Asymmetric Autocatalysis

    Arimasa Matsumoto; Yoshiyasu Kaimori; Mizuki Uchida; Haruna Omori; Tsuneomi Kawasaki; Kenso Soai

    Achiral inorganic gypsum (CaSO4 center dot 2H(2)O) triggers the asymmetric autocatalysis of pyrimidyl alkanol on its two-dimensional enantiotopic faces to give highly enantioenriched alkanol products with absolute configurations corresponding to the respective enantiotopic surfaces. This is the first example of highly enantioselective synthesis on the enantiotopic surface of an achiral mineral., WILEY-V C H VERLAG GMBH, Jan. 2017, ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 56 (2), 545 - 548, doi;web_of_science

    Scientific journal

  • Can the analyte-triggered asymmetric autocatalytic Soai reaction serve as a universal analytical tool for measuring enantiopurity and assigning absolute configuration?

    Christopher J. Welch; Kerstin Zawatzky; Alexey A. Makarov; Satoshi Fujiwara; Arimasa Matsumoto; Kenso Soai

    An investigation is reported on the use of the autocatalytic enantioselective Soai reaction, known to be influenced by the presence of a wide variety of chiral materials, as a generic tool for measuring the enantiopurity and absolute configuration of any substance. Good generality for the reaction across a small group of test analytes was observed, consistent with literature reports suggesting a diversity of compound types that can influence the stereochemical outcome of this reaction. Some trends in the absolute sense of stereochemical enrichment were noted, suggesting the possible utility of the approach for assigning absolute configuration to unknown compounds, by analogy to closely related species with known outcomes. Considerable variation was observed in the triggering strength of different enantiopure materials, an undesirable characteristic when dealing with mixtures containing minor impurities with strong triggering strength in the presence of major components with weak triggering strength. A strong tendency of the reaction toward an 'all or none' type of behavior makes the reaction most sensitive for detecting enantioenrichment close to zero. Consequently, the ability to discern modest from excellent enantioselectivity was relatively poor. While these properties limit the ability to obtain precise enantiopurity measurements in a simple single addition experiment, prospects may exist for more complex experimental setups that may potentially offer improved performance., ROYAL SOC CHEMISTRY, Jan. 2017, ORGANIC & BIOMOLECULAR CHEMISTRY, 15 (1), 96 - 101, doi;web_of_science

    Scientific journal

  • Unusual reversal of enantioselectivity in the asymmetric autocatalysis of pyrimidyl alkanol triggered by chiral aromatic alkanols and amines

    Arimasa Matusmoto; Satoshi Fujiwara; Yui Hiyoshi; Kerstin Zawatzky; Alexey A. Makarov; Christopher J. Welch; Kenso Soai

    Temperature dependent inversion of enantioselectivity in asymmetric catalysis is an interesting and somewhat unusual phenomenon. We have observed temperature dependent inversion of enantioselectivity in the asymmetric autocatalysis reaction when triggered by a wide scope of enantioenriched alcohols and amines. The addition reaction of diisopropylzinc to pyrimidine-5-carbaldehyde in the presence of enantiopure alcohols or amines affords the pyrimidyl alkanol product at 0 degrees C with high ee. However, lowering the reaction temperature to -44 degrees C affords the opposite enantioselectivity., ROYAL SOC CHEMISTRY, Jan. 2017, ORGANIC & BIOMOLECULAR CHEMISTRY, 15 (3), 555 - 558, doi;web_of_science

    Scientific journal

  • Asymmetric Induction by a Nitrogen N-14/N-15 Isotopomer in Conjunction with Asymmetric Autocatalysis

    Arimasa Matsumoto; Hanae Ozaki; Shunya Harada; Kyohei Tada; Tomohiro Ayugase; Hitomi Ozawa; Tsuneomi Kawasaki; Kenso Soai

    Chirality arising from isotope substitution, especially with atoms heavier than the hydrogen isotopes, is usually not considered a source of chirality in a chemical reaction. An N-2,N-2,N-3,N-3-tetramethyl-2,3-butanediamine containing nitrogen (N-14/N-15) isotope chirality was synthesized and it was revealed that this isotopically chiral diamine compound acts as a chiral initiator for asymmetric autocatalysis., WILEY-V C H VERLAG GMBH, Dec. 2016, ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 55 (49), 15246 - 15249, doi;web_of_science

    Scientific journal

  • Elucidation of the Structures of Asymmetric Autocatalyst Based on X-ray Crystallography

    Arimasa Matsumoto; Satoshi Fujiwara; Takaaki Abe; Atsushi Hara; Takayuki Tobita; Taisuke Sasagawa; Tsuneomi Kawasaki; Kenso Soai

    Much interest has been paid to the origin of homochirality, such as that of L-amino acids. The proposed origins of chirality have usually induced only low enantiomeric excess. Thus, asymmetric amplification by asymmetric autocatalysis has been invoked. Asymmetric autocatalysis of 5-pyrimidyl alkanol in the enantioselective addition of diisopropylzinc to pyrimidine-5-carbaldehyde is a unique example of amplification of chirality. Crystallization of possible intermediates, specifically zinc alkoxides of this 5-pyrimidyl alkanol, was investigated to obtain mechanistic insights into this reaction. Single-crystal X-ray crystallography of the formed zinc alkoxide crystals shows the existence of tetramer or higher oligomer structures in this asymmetric autocatalytic system., CHEMICAL SOC JAPAN, Oct. 2016, BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN, 89 (10), 1170 - 1177, doi;web_of_science

    Scientific journal

  • Determination of the absolute structure of the chiral crystal consisting of achiral dibutylhydroxytoluene and asymmetric autocatalysis triggered by this chiral crystal

    Arimasa Matsumoto; Sora Takeda; Shunya Harada; Kenso Soai

    Absolute structure is determined of chiral crystal composed of achiral dibutylhydroxytoluene (BHT, 2,6-di-tert-butyl-p-cresol) by single crystal X-ray diffraction and circular dichroism. Left-handed (M-) crystals exhibited a positive Cotton effect at a wavelength of approximately 288 nm observed using KBr disk [CD (+)288(Kbr)]. In contrast, right-handed (P-) crystals exhibited a negative Cotton effect at the same wavelength [CD(-)288(Kbr)]. Asymmetric autocatalysis is triggered by the chiral crystals of achiral BHT, i.e., M-(+)-BHT afforded (S)-pyrimidyl alkanol and P-(-)-BHT afforded (R)-pyrimidyl alkanol. 2016 The Author(s). Published by Elsevier Ltd., PERGAMON-ELSEVIER SCIENCE LTD, Oct. 2016, TETRAHEDRON-ASYMMETRY, 27 (19), 943 - 946, doi;web_of_science

    Scientific journal

  • Absolute Structure Determination of Chiral Crystals Consisting of Achiral Benzophenone with Single-crystal X-ray Diffraction and Its Correlation with Solid-state Circular Dichroism

    Arimasa Matsumoto; Sumeru Tsuchiya; Yuki Hagiwara; Kazuhiko Ishikawa; Hideko Koshima; Toru Asahi; Kenso Soai

    Achiral benzophenone is one of the simplest organic aromatic ketones that crystallize in the chiral form. The absolute structure of chiral crystals consisting of achiral benzophenone was firstly determined with single-crystal X-ray diffraction analysis and the absolute structure was successfully correlated with the solid-state circular dichroism spectra., CHEMICAL SOC JAPAN, May 2016, CHEMISTRY LETTERS, 45 (5), 526 - 528, doi;web_of_science

    Scientific journal

  • Crystal Structure of the Isopropylzinc Alkoxide of Pyrimidyl Alkanol: Mechanistic Insights for Asymmetric Autocatalysis with Amplification of Enantiomeric Excess

    Arimasa Matsumoto; Takaaki Abe; Atsushi Hara; Takayuki Tobita; Taisuke Sasagawa; Tsuneomi Kawasaki; Kenso Soai

    Asymmetric amplification during self-replication is a key feature that is used to explain the origin of homochirality. Asymmetric autocatalysis of pyrimidyl alkanol in the asymmetric addition of diisopropylzinc to pyrimidine-5-carbaldehyde is a unique example of this phenomenon. Crystallization of zinc alkoxides of this 5-pyrimidyl alkanol and single-crystal X-ray diffraction analysis of the alkoxide crystals reveal the existence of tetramer or higher oligomer structures in this asymmetric autocatalytic system., WILEY-V C H VERLAG GMBH, Dec. 2015, ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 54 (50), 15218 - 15221, doi;web_of_science

    Scientific journal

  • Asymmetric Autocatalysis Triggered by Chiral Crystal of Achiral Ethylenediamine Sulfate

    Arimasa Matsumoto; Takahiro Ide; Yoshiyasu Kaimori; Satoshi Fujiwara; Kenso Soai

    Achiral ethylenediamine forms chiral structures spontaneously when crystallized as the sulfate salt. By using these chiral crystals of ethylenediamine sulfate (ethylenediammonium sulfate), asymmetric autocatalysis of pyrimidyl alkanol affords a highly enantioenriched product with chirality that is determined by the chirality of the crystals., CHEMICAL SOC JAPAN, May 2015, CHEMISTRY LETTERS, 44 (5), 688 - 690, doi;web_of_science

    Scientific journal

  • Asymmetric induction by retgersite, nickel sulfate hexahydrate, in conjunction with asymmetric autocatalysis

    Arimasa Matsumoto; Hirokazu Ozawa; Ayako Inumaru; Kenso Soai

    Retgersite, nickel sulfate hexahydrate, forms a chiral crystal with space group P4(1)2(1)2 or P4(3)2(1)2. A chiral crystal of nickel sulfate hexahydrate was found to act as a chiral initiator of asymmetric autocatalysis, affording highly enantiomerically enriched pyrimidyl alkanols with the corresponding absolute configurations., ROYAL SOC CHEMISTRY, 2015, NEW JOURNAL OF CHEMISTRY, 39 (9), 6742 - 6745, doi;web_of_science

    Scientific journal

  • Helical mesoporous silica as an inorganic heterogeneous chiral trigger for asymmetric autocatalysis with amplification of enantiomeric excess

    Tsuneomi Kawasaki; Yuko Araki; Kunihiko Hatase; Kenta Suzuki; Arimasa Matsumoto; Toshiyuki Yokoi; Yoshihiro Kubota; Takashi Tatsumi; Kenso Soai

    Mesoporous silica has been used as a heterogeneous support for catalysts; however, asymmetric induction by the helicity of inorganic mesoporous silica itself has not yet been achieved. P- and M-helical mesoporous silica was found to act as a chiral inorganic trigger for asymmetric autocatalysis to afford (S) and (R)-pyrimidyl alkanol with >99.5% ee, respectively., ROYAL SOC CHEMISTRY, 2015, CHEMICAL COMMUNICATIONS, 51 (42), 8742 - 8744, doi;web_of_science

    Scientific journal

  • Asymmetric Induction by Retgersite, Nickel Sulfate Hexahydrate, in Conjunction with Asymmetric Autocatalysis

    A. Matsumoto; H. Ozawa; A. Inumaru; K. Soai

    2015, NEW JOURNAL OF CHEMISTRY, 51 (42), 8742 - 8744, doi

  • Asymmetric Autocatalysis of Pyrimidyl Alkanol and Its Application to the Study on the Origin of Homochirality

    Kenso Soai; Tsuneomi Kawasaki; Arimasa Matsumoto

    Conspectus Amplification of enantiomeric excess (ee) is a key feature for the chemical evolution of biological homochirality from the origin of chirality. We describe the amplification of ee in the asymmetric autocatalysis of 5-pyrimidyl alkanols in the reaction between diisopropylzinc (i-Pr2Zn) and pyrimidine-5-carbaldehydes. During the reaction, an extremely low ee (ca. 0.00005% ee) can be amplified to >99.5% ee, and therefore, the initial slightly major enantiomer is automultiplied by a factor of ca. 630000, while the initial slightly minor enantiomer is automultiplied by a factor of less than 1000. In addition, pyrimidyl alkanols with various substituents at the 2-position of the pyrimidine ring, 3-quinolyl alkanol, 5-carbamoyl-3-pyridyl alkanol, and large multifunctionalized pyrimidyl alkanols also act as highly efficient asymmetric autocatalysts in the addition of i-Pr2Zn to the corresponding aldehydes. The asymmetric autocatalysis of pyrimidyl alkanol can discriminate the chirality of various compounds. Chiral substances such as alcohols, amino acids, hydrocarbons, metal complexes, and heterogeneous chiral materials can act as chiral triggers for asymmetric autocatalysis to afford pyrimidyl alkanols with the corresponding absolute configuration of the initiator. This recognition ability of chiral compounds is extremely high, and chiral discrimination of a cryptochiral quaternary saturated hydrocarbon was established by applying asymmetric autocatalysis. By using the large amplification effect of the asymmetric autocatalysis, we can link various proposed origins of chirality with highly enantioenriched organic compounds in conjunction with asymmetric autocatalysis. Thus, a statistical fluctuation in ee of racemic compounds can be amplified to high ee by using asymmetric autocatalysis. Enantiomeric imbalance induced by irradiation of circularly polarized light can affect the enantioselectivity of asymmetric autocatalysis. The asymmetric autocatalysis was also triggered by the morphology of inorganic chiral crystals such as quartz, sodium chlorate, and cinnabar. Chiral organic crystals of achiral compounds also act as chiral initiators, and during the study of a crystal of cytosine, enantioselective chiral crystal phase transformation of the cytosine crystal was achieved by removal of the water of crystallization in an achiral monohydrate crystal. Enantioselective C-C bond formation was realized on the surfaces of achiral single crystals based on the oriented prochirality of achiral aldehydes. Furthermore, asymmetric autocatalysis of pyrimidyl alkanols is a highly sensitive reaction that can recognize and amplify the significantly small effect of a chiral compound arising solely from isotope substitution of hydrogen, carbon, and oxygen (D/H, (CC)-C-13-C-12, and O-18/O-16). These examples show that asymmetric autocatalysis with an amplification of chirality is a powerful tool for correlating the origin of chirality with highly enantioenriched organic compounds. Asymmetric autocatalysis using two b-amino alcohols reveals a reversal of enantioselectivity in the addition of i-Pr2Zn to aldehyde and is one approach toward understanding the mechanism of asymmetric dialkylzinc addition, where heteroaggregates act as the catalytic species., AMER CHEMICAL SOC, Dec. 2014, ACCOUNTS OF CHEMICAL RESEARCH, 47 (12), 3643 - 3654, doi;web_of_science

  • Self-Replication and Amplification of Enantiomeric Excess of Chiral Multifunctionalized Large Molecules by Asymmetric Autocatalysis

    Tsuneomi Kawasaki; Mai Nakaoda; Yutaro Takahashi; Yusuke Kanto; Nanako Kuruhara; Kenji Hosoi; Itaru Sato; Arimasa Matsumoto; Kenso Soai

    Self-replication of large chiral molecular architectures is one of the great challenges and interests in synthetic, systems, and prebiotic chemistry. Described herein is a new chemical system in which large chiral multifunctionalized molecules possess asymmetric autocatalytic self-replicating and self-improving abilities, that is, improvement of their enantioenrichment in addition to the diastereomeric ratio. The large chiral multifunctionalized molecules catalyze the production of themselves with the same structure, including the chirality of newly formed asymmetric carbon atoms, in the reaction of the corresponding achiral aldehydes and reagent. The chirality of the large multifunctionalized molecules controlled the enantioselectivity of the reaction in a highly selective manner to construct multiple asymmetric stereogenic centers in a single reaction., WILEY-V C H VERLAG GMBH, Oct. 2014, ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 53 (42), 11199 - 11202, doi;web_of_science

    Scientific journal

  • Asymmetric Autocatalysis Initiated by Finite Single-Wall Carbon Nanotube Molecules with Helical Chirality

    Shunpei Hitosugi; Arimasa Matsumoto; Yoshiyasu Kaimori; Ryosuke Iizuka; Kenso Soai; Hiroyuki Isobe

    An asymmetric autocatalysis reaction was initiated by a finite single-wall carbon nanotube molecule with helical chirality. The asymmetric induction was initiated by the chiral environment arising from the planar chirality of the tubular polyaromatic hydrocarbons., AMER CHEMICAL SOC, Feb. 2014, ORGANIC LETTERS, 16 (3), 645 - 647, doi;web_of_science

    Scientific journal

  • The Origins of Homochirality Examined by Using Asymmetric Autocatalysis

    Kenso Soai; Tsuneomi Kawasaki; Arimasa Matsumoto

    Pyrimidyl alkanol was found to act as an asymmetric autocatalyst in the enantioselective addition of diisopropylzinc to pyrimidine-5-carbaldehyde. Asymmetric autocatalysis of 2-alkynylpyrimidyl alkanol with an extremely low enantiomeric excess (ca. 0.00005% ee) exhibits enormous asymmetric amplification to afford the same compound with >99.5% ee. This asymmetric autocatalysis with amplification of ee has been employed to examine the validity of proposed theories of the origins of homochirality. Circularly polarized light, quartz, sodium chlorate, cinnabar, chiral organic crystals and spontaneous absolute asymmetric synthesis were considered as possible candidates for the origin of chirality; each could act as a chiral source in asymmetric autocatalysis. Asymmetric autocatalysis can discriminate the isotope chirality arising from the small difference between carbon (carbon-13/carbon-12) and hydrogen (D/H) isotopes. Cryptochiral compounds were also discriminated by asymmetric autocatalysis., WILEY-V C H VERLAG GMBH, Feb. 2014, CHEMICAL RECORD, 14 (1), 70 - 83, doi;web_of_science

    Scientific journal

  • Enantiodivergent formation of a chiral cytosine crystal by removal of crystal water from an achiral monohydrate crystal under reduced pressure

    Hiroko Mineki; Yoshiyasu Kaimori; Tsuneomi Kawasaki; Arimasa Matsumoto; Kenso Soai

    An achiral nucleobase cytosine forms an achiral monohydrate crystal (space group: P21/c) by crystallization from a water solution. It was found that the removal of crystal water under reduced pressure at room temperature afforded a chiral crystal of anhydrous cytosine (P212 121). The crystal chirality of anhydrous cytosine corresponds to the enantiotopic crystal face of the achiral monohydrate therefore, when the enantiotopic b1-face is exposed to the reduced pressure, dehydration occurred in the direction from the b1-face to provide [CD(+)310KBr]-cytosine crystal. In contrast, dehydration from the b2-face gave the opposite enantiomorphous [CD(-)310 KBr]-cytosine crystal. The correlation between enantiotopic faces and the formed crystal chirality is opposite to that from dehydration by heating. The formed chiral cytosine crystals act as a chiral trigger for asymmetric autocatalysis with enantioenrichment amplification of pyrimidylalkanol., 30 Nov. 2013, Tetrahedron Asymmetry, 24 (21-22), 1365 - 1367, doi

    Scientific journal

  • Asymmetric Autocatalysis Induced by Cinnabar: Observation of the Enantioselective Adsorption of a 5-Pyrimidyl Alkanol on the Crystal Surface

    Hitoshi Shindo; Yusuke Shirota; Kaori Niki; Tsuneomi Kawasaki; Kenta Suzuki; Yuko Araki; Arimasa Matsumoto; Kenso Soai

    WILEY-V C H VERLAG GMBH, Aug. 2013, ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 52 (35), 9135 - 9138, doi;web_of_science

    Scientific journal

  • Enantioselective Synthesis Induced by the Helical Molecular Arrangement in the Chiral Crystal of Achiral Tris(2-hydroxyethyl) 1,3,5-Benzenetricarboxylate in Conjunction with Asymmetric Autocatalysis

    Tsuneomi Kawasaki; Mizuki Uchida; Yoshiyasu Kaimori; Taisuke Sasagawa; Arimasa Matsumoto; Kenso Soai

    5-Pyrimidyl alkanol with an enantiomeric excess of up to >99.5% was formed using chiral crystals of achiral tris(2-hydroxyethyl) 1,3,5-benzenetricarboxylate as a chiral initiator. In the enantioselective addition of diisopropylzinc to pyrimidine-5-carbaldehyde, the helicity of the molecular arrangement of achiral tricarboxylate in the crystalline state could be successfully used as a source of chirality to afford enantioen-riched alkanol in conjunction with asymmetric autocatalysis with amplification of enantiomeric excess., CHEMICAL SOC JAPAN, Jul. 2013, CHEMISTRY LETTERS, 42 (7), 711 - 713, doi;web_of_science

    Scientific journal

  • Asymmetric autocatalysis triggered by oxygen isotopically chiral glycerin

    Arimasa Matsumoto; Shotaro Oji; Shizuka Takano; Kyohei Tada; Tsuneomi Kawasaki; Kenso Soai

    Chiral (S)- and (R)-18O-glycerin induces enantioselective addition of diisopropylzinc to pyrimidine-5-carbaldehyde, and the subsequent asymmetric autocatalysis affords (R)- and (S)-pyrimidyl alkanol with high enantiomeric excess, respectively. © The Royal Society of Chemistry 2013., 14 May 2013, Organic and Biomolecular Chemistry, 11 (18), 2928 - 2931, doi

    Scientific journal

  • β-Arylation of carboxamides via iron-catalyzed C(sp3)-H bond activation

    Rui Shang; Laurean Ilies; Arimasa Matsumoto; Eiichi Nakamura

    A 2,2-disubstituted propionamide bearing an 8-aminoquinolinyl group as the amide moiety can be arylated at the β-methyl position with an organozinc reagent in the presence of an organic oxidant, a catalytic amount of an iron salt, and a biphosphine ligand at 50 C. Various features of selectivity and reactivity suggest the formation of an organometallic intermediate via rate-determining C-H bond cleavage rather than a free-radical-type reaction pathway. © 2013 American Chemical Society., 24 Apr. 2013, Journal of the American Chemical Society, 135 (16), 6030 - 6032, doi

    Scientific journal

  • Synthesis of Polysubstituted Naphthalenes by Iron-Catalyzed [2+2+2] Annulation of Grignard Reagents with Alkynes

    Laurean Ilies; Arimasa Matsumoto; Motoaki Kobayashi; Naohiko Yoshikai; Eiichi Nakamura

    Iron catalyzes the oxidative [2+2+2] annulation of an arylmagnesium compound with two molecules of an internal alkyne via C-H bond activation at 0 degrees C to produce polysubstituted naphthalene., GEORG THIEME VERLAG KG, Oct. 2012, SYNLETT, 23 (16), 2381 - 2384, doi;web_of_science

    Scientific journal

  • Iron-Catalyzed Nitrogen-Directed Coupling of Arene and Aryl Bromides Mediated by Metallic Magnesium

    Laurean Ilies; Motoaki Kobayashi; Arimasa Matsumoto; Naohiko Yoshikai; Eiichi Nakamura

    2-Arylpyridines, 2-alkenylpyridine, and aromatic imines can be coupled with aryl bromides in the presence of an iron catalyst, metallic magnesium, a diamine ligand and an organic dihalide oxidant at 0 degrees C. The use of a 1:1 mixture of tetrahydrofuran and 1,4-dioxane is essential for this C-H bond activation reaction. The reaction has wider scope of the substrate compared with the reaction using a separately prepared Grignard reagent, and proceeds with lower catalyst loading (2.5 mol%)., WILEY-V C H VERLAG GMBH, Mar. 2012, ADVANCED SYNTHESIS & CATALYSIS, 354 (4), 593 - 596, doi;web_of_science

    Scientific journal

  • Asymmetric autocatalysis initiated by achiral nucleic acid base adenine: implications on the origin of homochirality of biomolecules

    Hiroko Mineki; Taichi Hanasaki; Arimasa Matsumoto; Tsuneomi Kawasaki; Kenso Soai

    Enantiomorphous crystals of adeninium dinitrate acted as the source of chirality in asymmetric autocatalysis producing highly enantioenriched (S)- and (R)-5-pyrimidyl alkanols, with the absolute configurations corresponding to that of crystals., ROYAL SOC CHEMISTRY, 2012, CHEMICAL COMMUNICATIONS, 48 (85), 10538 - 10540, doi;web_of_science

    Scientific journal

  • Phenanthrene Synthesis by Iron-Catalyzed [4+2] Benzannulation between Alkyne and Biaryl or 2-Alkenylphenyl Grignard Reagent

    Arimasa Matsumoto; Laurean Ilies; Eiichi Nakamura

    The [4 + 2] benzannulation reaction of internal or terminal alkynes with 2-biaryl, 2-heteroarylphenyl, or 2-alkenylphenyl Grignard reagents in the presence of Fe(acac)3, 4,4'-di-tert-butyl-2,2'-bipyridyl, and 1 ,2-dichloro-2-methylpropane takes place at room temperature in I h to give 9-substituted or 9,10-disubstituted phenanthrenes and congeners in moderate to excellent yields. The reaction tolerates sensitive functional groups such as bromide and olefin. When applied to a 1,3-diyne, the annulation reaction takes place on both acetylenic moieties to give a bisphenanthrene derivative., AMER CHEMICAL SOC, May 2011, JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 133 (17), 6557 - 6559, doi;web_of_science

    Scientific journal

  • Iron-Catalyzed C-C Bond Formation at alpha-Position of Aliphatic Amines via C-H Bond Activation through 1,5-Hydrogen Transfer

    Naohiko Yoshikai; Adam Mieczkowski; Arimasa Matsumoto; Laurean Ilies; Eiichi Nakamura

    C-C bond formation reactions that take place through organoiron species sometimes exhibit radical-like character. The reaction of N-(2-iodophenylmethyl)dialkylamine with a Grignard or diorganozinc reagent in the presence of a catalytic amount of Fe(acac)3 gives the product resulting from arylation, alkenylation, or alkylation of the sp(3) C-H bond next to the amine group in good to excellent yield. Mechanistic studies including labeling experiments indicate that the reaction involves radical translocation triggered by the formation of a radical-like species by removal of the iodide group., AMER CHEMICAL SOC, Apr. 2010, JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 132 (16), 5568 - +, doi;web_of_science

    Scientific journal

  • Iron-Catalyzed Direct Arylation of Aryl Pyridines and Imines Using Oxygen as an Oxidant

    Naohiko Yoshikai; Arimasa Matsumoto; Jakob Norinder; Eiichi Nakamura

    An iron-catalyzed ortho C-H bond arylation reaction of an aryl pyridine or imine with an arylzinc reagent, which previously required the use of a rather expensive organodichloride as an oxidant, can now be achieved under oxygen atmosphere. By slowly introducing oxygen into the reaction, oxidative cross-coupling of the two reactants took place smoothly to give a biaryl product in moderate to good yield., GEORG THIEME VERLAG KG, Jan. 2010, SYNLETT, (2), 313 - 316, doi;web_of_science

    Scientific journal

  • Iron-Catalyzed Chemoselective ortho Arylation of Aryl Imines by Directed C-H Bond Activation

    Naohiko Yoshikai; Arimasa Matsumoto; Jakob Norinder; Eiichi Nakamura

    WILEY-V C H VERLAG GMBH, 2009, ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 48 (16), 2925 - 2928, doi;web_of_science

    Scientific journal

  • Iron-catalyzed direct arylation through directed C-H bond activation

    Jakob Norinder; Arimasa Matsumoto; Naohiko Yoshikai; Eiichi Nakamura

    An iron-catalyzed C-C bond formation reaction of a nitrogencontaining aromatic compound with an arylzinc reagent takes place at 0 degrees C in a good to quantitative yield. The reaction involves a C-H bond activation directed by a neighboring nitrogen atom. The important additives in this reaction are 1,10-phenanthroline, tetramethylethylenediamine, and 1,2-dichloro2-methylpropane, in the absence of which a very low product yield was observed., AMER CHEMICAL SOC, May 2008, JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 130 (18), 5858 - +, doi;web_of_science

    Scientific journal

  • Chiral approach to investigate mechanism of highly efficient thermally activated delayed fluorescence

    Kikuya Hayashi; Arimasa Matsumoto; Shuzo Hirata

    Cancellation of the Cotton effect depending on vibrations of a chiral orthogonal donor–acceptor structure identifies a mechanism of highly efficient delayed fluorescence.

    , Royal Society of Chemistry (RSC), 2021, Chemical Communications, 57 (14), 1738 - 1741, doi;url

    Scientific journal

  • Structure and electrochemical properties of (µ-O)2Mn2(III,III) and (µ-O)2Mn2(III,IV) complexes supported by pyridine-, quinoline-, isoquinoline- and quinoxaline-based tetranitrogen ligands

    Yuji Mikata; Yasuko Kuroda; Kyoko Naito; Kana Murakami; Chihiro Yamamoto; Shoko Yabe; Shizuka Yonemura; Arimasa Matsumoto; Hajime Katano

    Seven new bis(µ-oxo) dimanganese complexes with Mn2(III,III) or Mn2(III,IV) oxidation states were prepared using quinoline- and isoquinoline-based tetraamine ligands. The structures of the ligands include ethylenediamine, trans-1,2-cyclohexanediamine and tripodal amine,...

    , Royal Society of Chemistry (RSC), 2021, Dalton Transactions, doi;url

    Scientific journal

  • Conversion of (µ-OH)2Mn2(II,II) complex to (µ-O)2Mn2(III,III) core supported by a quinoxaline-based tetranitrogen ligand

    Yuji Mikata; Kana Murakami; Ayaka Ochi; Fumie Nakagaki; Kyoko Naito; Arimasa Matsumoto; Ryoji Mitsuhashi; Masahiro Mikuriya

    Elsevier BV, Sep. 2020, Inorganica Chimica Acta, 509, 119688 - 119688, doi

    Scientific journal

  • Asymmetric autocatalysis triggered by triglycine sulfate with switchable chirality by altering the direction of the applied electric field

    Tsuneomi Kawasaki; Yoshiyasu Kaimori; Seiya Shimada; Natsuki Hara; Susumu Sato; Kenta Suzuki; Toru Asahi; Arimasa Matsumoto; Kenso Soai

    In asymmetric autocatalysis with amplification of ee, molecular chirality of highly enantioenriched organic compounds is controlled by a crystal TGS, whose chirality is switchable by changing the direction of the applied static electric field.

    , Royal Society of Chemistry (RSC), 2021, Chemical Communications, 57 (49), 5999 - 6002, doi;url

    Scientific journal

MISC

  • Asymmetric Autocatalysis and the Elucidation of the Origin of Homochirality

    松本 有正; 松本有正; そ合憲三

    2016, ファインケミカル, 45 (2), 58 - 67

  • 不斉自己触媒反応を用いたキラル化学 ー同位体置換キラル化合物が誘起するエナンチオ選択的反応ー

    松本 有正; 川崎常臣; 松本有正; そ合憲三

    2015, 化学工業, 66, 133 - 138

  • Absolute configuration analysis of organic compounds by single crystal X-ray diffraction

    Arimasa Matsumoto

    Thanks to the development of automation systems and programs for single crystal X-ray diffraction analysis, X-ray structure analysis have become a familiar technic for organic chemists to obtain structural information. However, determination of the absolute configuration of organic compounds only including light-atom (C, H, N, O) by X-ray diffraction have been a difficult topic due to the weak resonant scattering from light atoms. The main purpose of this review is to introduce recent developments of absolute structure determination method by X-ray structure analysis. New algorisms, such as Hooft parameter and Parsons parameter, make it possible to determine the absolute configuration of organic compound by typical X-ray diffractometer without any special equipment., Society of Synthetic Organic Chemistry, 2015, Yuki Gosei Kagaku Kyokaishi/Journal of Synthetic Organic Chemistry, 73 (7), 755 - 761, doi

  • Approaches toward the origin of homochirality using the synthetic organic chemistry - Asymmetric autocatalysis with amplification of enantiomeric excess

    Tsuneomi Kawasaki; Itaru Sato; Hiroko Mineki; Arimasa Matsumoto; Kenso Soai

    Asymmetric autocatalysis with amplification of enantiomeric excess is found in the enantiose-lective addition of diisopropylzinc to pyrimidine-5- carbaldehyde using pyrimidyl alkanol as an asymmetric autocatalyst. Asymmetric autocatalysis has been employed as a method for clarifying the origin of homochirality. Circularly polarized light, quartz and statistical fluctuation of enantio-meric imbalance act as chiral triggers for asymmetric autocatalysis to afford highly enantioen-riched products. We have investigated the asymmetric autocatalysis using chiral crystals formed from achiral and racemic compounds as the origins of chirality. Absolute control of the crystal chirality of cytosine was achieved by the removal of crystal water of achiral cytosine monohydrate. Enantioselective carbon-carbon bond formation on the enantiotopic crystal face of aldehyde was established by using the vapor of diisopropylzinc. In addition, asymmetric autocatalysis triggered by chiral compounds arising from H, C and O isotopes substitution has been achieved. Reversal phenomena of enantioselectivity were observed in β-amino alcohol catalyzed dialkylzinc addition to aldehyde by using the mixture of two different β-amino alcohols as chiral ligands., 2013, Yuki Gosei Kagaku Kyokaishi/Journal of Synthetic Organic Chemistry, 71 (2), 109 - 123, doi

    Book review

  • Asymmetric autocatalysis Pathway to the biological homochirality

    Tsuneomi Kawasaki; Arimasa Matsumoto; Kenso Soai

    Amplifi cation of enantiomeric excess (ee) is a key feature for the chemical evolution of biological homochirality from the viewpoint of the origin of chirality. We describe the amplifi cation of ee in asymmetric autocatalysis of 5-pyrimidyl alkanol in the reaction between diisopropylzinc and pyrimidine-5-carbaldehyde. During the asymmetric autocatalysis, very low ee (ca. 0.00005 %) can be amplifi ed to become more than 99.5% ee. Because the proposed origins of chirality, such as circularly polarized light, chiral inorganic quartz and statistical fluctuations of ee in racemic compounds, can initiate asymmetric autocatalysis with amplifi cation of ee, these proposed origins of chirality can be linked with enantiopure organic compounds via asymmetric autocatalysis. Spontaneous absolute asymmetric synthesis has been achieved for the first time. In addition, we describe how the crystal chirality of cytosine generated by the dehydration of crystal water can trigger asymmetric autocatalysis. Thus, the achiral nucleobase, cytosine, is one of the candidates for the origin of chirality. Asymmetric autocatalysis can correlate the chiral isotopomers to the highly enantioenriched 5-pyrimidyl alkanol, that is, D/H-, C-13/C-12- and O-18/O-16-substituted chiral isotopomers can act as chiral initiators of asymmetric autocatalysis. Therefore, the tiny isotope chirality could be another explanation for the origin of chirality., TEKNOSCIENZE PUBL, Sep. 2012, CHIMICA OGGI-CHEMISTRY TODAY, 30 (5), 10 - 13, web_of_science

    Book review

  • Asymmetric Autocatalysis. Pathway to The Biological Homochirality

    Matsumoto Arimasa; Tsuneomi Kawasaki; Arimasa Matsumoto; Kenso Soai

    2012, CHIMICA OGGI-CHEMISTRY TODAY, 30 (5), 10 - 13

Books etc

  • Iron-Catalyzed Synthesis of Fused Aromatic Compounds via C-H Bond Activation

    Springer, 2014 (ISBN: 9784431549277)

  • Iron-Catalyzed Synthesis of Fused Aromatic Compounds via C-H Bond Activation

    Springer, 2014 (ISBN: 9784431549277)

  • CSJ Current Review 13 キラル化学 15章 不斉自己増殖とホモキラリティの起源

    日本化学会, 2013 (ISBN: 9784759813739)

Presentations

  • Mechanistic Study of Asymmetric Autocatalysis Using CD spectrum: Temperature and Concentration Effect on Catalysts Aggregation Structure

    Arimasa Matsumoto, Ayame Tanaka, Yuji Mikata, Kenso Soai

    Chirality 2019, 15 Jul. 2019, 14 Jul. 2019, 17 Jul. 2019

  • Mechanistic Insight of Asymmetric Autocatalysis of Pyrimidyl Alkanol by Structure Analysis of Zinc Alkoxide Complexes

    ICPAC2018, 2018

  • Chirality Generation by Crystal Phase Transition of Achiral Benzophenone Derivatives

    Chirality 2017, 2017

  • Achiral to Chiral Crystal Phase Transition of Achiral Achiral to Chiral Crystal Phase Transition of Benzophenone Derivatives and Asymmetric Autocatalysis Initiated by the Crystal Chirality

    錯体化学会第67回討論会, 2017

  • Chirality Generation by Crystal Phase Transition of Achiral Benzophenone Derivatives

    Chirality 2017, 2017

  • Achiral to Chiral Crystal Phase Transition of Achiral Achiral to Chiral Crystal Phase Transition of Benzophenone Derivatives and Asymmetric Autocatalysis Initiated by the Crystal Chirality

    The 67th Confeence of Japan Society of Coordination Chemistry, 2017

Association Memberships

  • 錯体化学会

  • 日本化学会

  • 有機合成化学協会

  • 近畿化学協会 有機金属部会



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