The Chemical Record

Cover image for Vol. 14 Issue 1

Special Issue: 40 Years of the Mukaiyama Aldol Reaction

February 2014

Volume 14, Issue 1

Pages 1–227

  1. Cover Picture

    1. Top of page
    2. Cover Picture
    3. Masthead
    4. Graphical Abstract
    5. Editorial
    6. Guest Editorial
    7. Personal Accounts
    8. Records and Challenges
    9. Collage/List of Essays
    10. Essay
    11. Page Table/Nobelist List
    12. Autograph Book Pages
    1. You have free access to this content
      Cover Picture (page 1)

      Version of Record online: 26 FEB 2014 | DOI: 10.1002/tcr.201400101

      Thumbnail image of graphical abstract

      In addition to Personal Accounts and world records, this issue features the Nozoe Autograph Book series. All Essays and the interactive website for the Nozoe Autograph Book project are found at: www.tcr.wiley-vch.de/nozoe.

  2. Masthead

    1. Top of page
    2. Cover Picture
    3. Masthead
    4. Graphical Abstract
    5. Editorial
    6. Guest Editorial
    7. Personal Accounts
    8. Records and Challenges
    9. Collage/List of Essays
    10. Essay
    11. Page Table/Nobelist List
    12. Autograph Book Pages
    1. Masthead (page 2)

      Version of Record online: 26 FEB 2014 | DOI: 10.1002/tcr.201400102

  3. Graphical Abstract

    1. Top of page
    2. Cover Picture
    3. Masthead
    4. Graphical Abstract
    5. Editorial
    6. Guest Editorial
    7. Personal Accounts
    8. Records and Challenges
    9. Collage/List of Essays
    10. Essay
    11. Page Table/Nobelist List
    12. Autograph Book Pages
    1. Graphical Abstract: Chem. 1/2014 (pages 3–8)

      Version of Record online: 26 FEB 2014 | DOI: 10.1002/tcr.201400103

  4. Editorial

    1. Top of page
    2. Cover Picture
    3. Masthead
    4. Graphical Abstract
    5. Editorial
    6. Guest Editorial
    7. Personal Accounts
    8. Records and Challenges
    9. Collage/List of Essays
    10. Essay
    11. Page Table/Nobelist List
    12. Autograph Book Pages
    1. You have free access to this content
      Lasting Legacies (pages 9–11)

      Brian P. Johnson

      Version of Record online: 26 FEB 2014 | DOI: 10.1002/tcr.201410001

  5. Guest Editorial

    1. Top of page
    2. Cover Picture
    3. Masthead
    4. Graphical Abstract
    5. Editorial
    6. Guest Editorial
    7. Personal Accounts
    8. Records and Challenges
    9. Collage/List of Essays
    10. Essay
    11. Page Table/Nobelist List
    12. Autograph Book Pages
    1. You have free access to this content
  6. Personal Accounts

    1. Top of page
    2. Cover Picture
    3. Masthead
    4. Graphical Abstract
    5. Editorial
    6. Guest Editorial
    7. Personal Accounts
    8. Records and Challenges
    9. Collage/List of Essays
    10. Essay
    11. Page Table/Nobelist List
    12. Autograph Book Pages
    1. Synthesis, Double-Helix Formation, and Higher-Assembly Formation of Chiral Polycyclic Aromatic Compounds: Conceptual Development of Polyketide Aldol Synthesis (pages 15–27)

      Masahiko Yamaguchi, Masanori Shigeno, Nozomi Saito and Koji Yamamoto

      Version of Record online: 16 DEC 2013 | DOI: 10.1002/tcr.201300014

      Thumbnail image of graphical abstract

      Polycyclic aromatic compounds are a group of important substances in chemistry, and the study of their properties is a subject of interest in the development of drugs and materials. We have been conducting studies to develop chiral polycyclic aromatic compounds, i.e., helicenes and equatorenes. These helical molecules showed notable aggregate-forming properties and the capability for chiral recognition exerted by noncovalent bond interactions, which were not observed in compounds with central chirality. Homo- and hetero-double-helix-forming helicene oligomers were developed, and the latter self-assembled to form gels and vesicles. In this article, we describe such hierarchical studies of polycyclic aromatic compounds, which were started from polyketide aldol synthesis.

    2. Total Synthesis of Hibarimicinone, a v-Src Tyrosine Kinase Inhibitor Possessing the Pseudo-Dimer Structure of Tetracycline (pages 28–40)

      Kuniaki Tatsuta and Seijiro Hosokawa

      Version of Record online: 19 DEC 2013 | DOI: 10.1002/tcr.201300020

      Thumbnail image of graphical abstract

      The total synthesis of hibarimicinone, a potent v-Src tyrosine kinase inhibitor, has been achieved. The key step to constructing the eight-ring skeleton was the double Michael–Dieckmann-type cyclization (Hauser annulation) using a thiolactone pseudo-dimer. The ABCD-ring moiety including the bridging ether was constructed by a strategy including oxidation of the C-ring hydroquinone and the subsequent transfer of the oxidation stage to the neighboring ring. The atropisomer of hibarimicinone was also synthesized to confirm the structure of the natural product.

    3. Triazole-Linked Analogues of DNA and RNA (TLDNA and TLRNA): Synthesis and Functions (pages 41–51)

      Hiroyuki Isobe and Tomoko Fujino

      Version of Record online: 19 DEC 2013 | DOI: 10.1002/tcr.201300023

      Thumbnail image of graphical abstract

      Click chemistry has allowed us access to DNA and RNA analogues with non-natural triazole internucleoside linkages. The bond periodicity of the oligonucleotides was designed to enforce duplex formation with natural congeners, and the non-cleavable linkages protect the oligomers against nuclease digestion. The progress of these triazole-linked analogues over the past five years is reviewed. Reinforced by their synthetic robustness, these analogues may find various uses as tools for exploratory research.

    4. Boron Enolate Chemistry toward the Syntheses of Polyketide Stereotetrads (pages 52–61)

      Ari M. P. Koskinen

      Version of Record online: 13 JAN 2014 | DOI: 10.1002/tcr.201300033

      Thumbnail image of graphical abstract

      Today nearly 10000 polyketides are known, and of them about 600 contain the tripropionate unit with a stereotetrad, four contiguous stereocenters with alternating methyl and hydroxyl substituents in the main chain. On the basis of their relative stereochemistry these can be classified into eight structural types. In 1976 Mukaiyama described mild enolate formation by treatment of a ketone with dibutylboron triflate in the presence of a tertiary amine, in a paper that was to make a major impact on the development of the aldol reaction. The versatility of the Mukaiyama boron-mediated aldol reaction is showcased with examples from total syntheses.

    5. Carbon Dioxide Incorporation into Alkyne Compounds Mediated by Silver Catalysts (pages 62–69)

      Satoshi Kikuchi and Tohru Yamada

      Version of Record online: 13 JAN 2014 | DOI: 10.1002/tcr.201300025

      Thumbnail image of graphical abstract

      A silver salt and base catalyst system was applied to CO2 incorporation with C–C bond formation to afford the corresponding γ-lactone derivatives in good to high yields. This catalyst system is an efficient approach to the synthesis of benzoxazin-2-one derivatives and 4-hydroxyquinolin-2(1H)-one derivatives from alkynylanilines with carbon dioxide.

    6. The Origins of Homochirality Examined by Using Asymmetric Autocatalysis (pages 70–83)

      Kenso Soai, Tsuneomi Kawasaki and Arimasa Matsumoto

      Version of Record online: 22 JAN 2014 | DOI: 10.1002/tcr.201300028

      Thumbnail image of graphical abstract

      Asymmetric autocatalysis is a reaction in which the chiral product acts as an asymmetric catalyst to give more of itself of the same absolute configuration. Asymmetric autocatalysis of 2-alkynylpyrimidyl alkanol in the enantioselective addition of diisopropylzinc exhibits enormous asymmetric amplification. This asymmetric autocatalysis with amplification of ee can discriminate the small enantiomeric imbalance induced by the proposed candidates for the origin of chirality, such as circularly polarized light, inorganic and organic chiral crystals, spontaneous absolute asymmetric synthesis, and isotope chirality.

    7. Organoplatinum-Mediated Synthesis of Cyclic π-Conjugated Molecules: Towards a New Era of Three-Dimensional Aromatic Compounds (pages 84–100)

      Shigeru Yamago, Eiichi Kayahara and Takahiro Iwamoto

      Version of Record online: 22 JAN 2014 | DOI: 10.1002/tcr.201300035

      Thumbnail image of graphical abstract

      Several cyclic π-conjugated molecules, as exemplified by cycloparaphenylenes (CPPs) and a cage-like 3D molecule, were synthesized based on the platinum-mediated assembly of π-units to form closed-cage compounds, from which reductive elimination of platinum gave the target molecule. The assembly of π-units by this method mimics the self-assembly process for the formation of supramolecular ligand–metal complexes. Furthermore, despite the high strain energy of the target molecule, reductive elimination of platinum successfully took place with high efficiency. Several size-dependent physical properties of CPPs, namely the photophysical, redox, and host–guest chemistries, are also described.

    8. Carboxylic Acid Free Novel Isocyanide-Based Reactions (pages 101–116)

      Takahiro Soeta and Yutaka Ukaji

      Version of Record online: 22 JAN 2014 | DOI: 10.1002/tcr.201300021

      Thumbnail image of graphical abstract

      In the search for practical new routes to drug-like and heterocyclic compounds, we have designed novel Passerini- and Ugi-type reaction systems where the carboxylic acid component has been replaced by compounds (Z–X) containing an electrophilic (Z) and a nucleophilic group (X). Based on this concept, we have developed the O-silylative Passerini reaction and the borinic acid catalyzed α-addition of isocyanides to aldehydes and water, as well as the addition reaction of isocyanides to nitrones in the presence of TMSCl to afford 1,2,3,4-tetrahydroisoquinoline-1-carboxyamides. Furthermore, a novel [5+1] cycloaddition of isocyanide was explored with C,N-cyclic N′-acyl azomethine imines as a “1,5-dipole”.

    9. Asymmetric Nitrene Transfer Reactions: Sulfimidation, Aziridination and C–H Amination Using Azide Compounds as Nitrene Precursors (pages 117–129)

      Tatsuya Uchida and Tsutomu Katsuki

      Version of Record online: 22 JAN 2014 | DOI: 10.1002/tcr.201300027

      Thumbnail image of graphical abstract

      Ru(CO)–salen complexes decompose azide compounds, atom-efficient nitrene precursors, under mild conditions and catalyze asymmetric nitrene transfer reactions such as sulfimidation, olefin aziridination and C–H amination in highly enantioselective manners. The reactions are chemoselective and the C–H amination occurs at benzylic and allylic positions in a highly regioselective manner. For example, 1-ethyl-4-(n-propyl)benzene is aminated only at the benzylic position of the ethyl group. The appropriate tuning of salen ligands, especially the aryl substituents at C2", is essential for obtaining high enantio- and regioselectivity. Ir–salen complexes are also efficient catalysts for the intramolecular C–H amination reaction.

    10. Development of Chiral Catalysts for Mukaiyama Aldol Reactions in Aqueous Media (pages 130–143)

      Taku Kitanosono and Shū Kobayashi

      Version of Record online: 22 JAN 2014 | DOI: 10.1002/tcr.201300040

      Thumbnail image of graphical abstract

      Water-compatible iron(II) and bismuth(III) Lewis acids catalyze asymmetric Mukaiyama aldol reactions under mild conditions with broad substrate tolerance, leading to widely applicable and versatile catalytic systems in aqueous media. The superiority of this methodology over conventional methods is demonstrated in terms of high catalytic activity, experimental simplicity, facile synthesis of the chiral ligand, and a wide substrate range that includes aqueous aldehydes, for which the stereochemistry had been regarded as difficult to control. The reaction did not proceed at all without use of water. In the postulated mechanism, water plays prominent roles in activating substrates, facilitating catalytic turnover, and stabilizing rigid transition states composed of metal complexes and reactants through entropy-driven aggregation derived from the highest cohesive energy density.

    11. Asymmetric Mukaiyama Aldol Reactions Using Chiral Diamine–Coordinated Sn(II) Triflate: Development and Application to Natural Product Synthesis (pages 144–183)

      Isamu Shiina

      Version of Record online: 25 JAN 2014 | DOI: 10.1002/tcr.201300022

      Thumbnail image of graphical abstract

      Asymmetric total syntheses of various natural products using Sn(II) Lewis acids consisting of chiral diamines derived from l- or d-proline with Sn(OTf)2 were established. In this Personal Account, we demonstrate the wide utility and great versatility of aldol and related addition reactions mediated by the chiral diamine–Sn(OTf)2 complex in the preparation of a number of optically active β-hydroxy carbonyl units (aldols).

  7. Records and Challenges

    1. Top of page
    2. Cover Picture
    3. Masthead
    4. Graphical Abstract
    5. Editorial
    6. Guest Editorial
    7. Personal Accounts
    8. Records and Challenges
    9. Collage/List of Essays
    10. Essay
    11. Page Table/Nobelist List
    12. Autograph Book Pages
    1. Record of Records (pages 184–211)

      Version of Record online: 26 FEB 2014 | DOI: 10.1002/tcr.201400104

  8. Collage/List of Essays

    1. Top of page
    2. Cover Picture
    3. Masthead
    4. Graphical Abstract
    5. Editorial
    6. Guest Editorial
    7. Personal Accounts
    8. Records and Challenges
    9. Collage/List of Essays
    10. Essay
    11. Page Table/Nobelist List
    12. Autograph Book Pages
    1. You have free access to this content
  9. Essay

    1. Top of page
    2. Cover Picture
    3. Masthead
    4. Graphical Abstract
    5. Editorial
    6. Guest Editorial
    7. Personal Accounts
    8. Records and Challenges
    9. Collage/List of Essays
    10. Essay
    11. Page Table/Nobelist List
    12. Autograph Book Pages
    1. You have free access to this content
      Prospecting in Hückel-space: From Hinokitiol to Non-benzenoid Organic Electronics (pages 214–225)

      John D. Tovar

      Version of Record online: 20 DEC 2013 | DOI: 10.1002/tcr.201300034

      Thumbnail image of graphical abstract

      Artistic foundations for emerging organic electronics: The Essay by J. D. Tovar describes contemporary efforts to explore compounds with non-benzenoid aromatic building blocks, as well as carbon networks of a more benzenoid character, on the basis of examples which fortuitously appeared in the Nozoe Autograph Books. This Essay and the interactive website that accompanies the Nozoe Autograph Book project are available free-access for at least a three-year period at http://www.tcr.wiley-vch.de/nozoe.

  10. Page Table/Nobelist List

    1. Top of page
    2. Cover Picture
    3. Masthead
    4. Graphical Abstract
    5. Editorial
    6. Guest Editorial
    7. Personal Accounts
    8. Records and Challenges
    9. Collage/List of Essays
    10. Essay
    11. Page Table/Nobelist List
    12. Autograph Book Pages
    1. You have free access to this content
  11. Autograph Book Pages

    1. Top of page
    2. Cover Picture
    3. Masthead
    4. Graphical Abstract
    5. Editorial
    6. Guest Editorial
    7. Personal Accounts
    8. Records and Challenges
    9. Collage/List of Essays
    10. Essay
    11. Page Table/Nobelist List
    12. Autograph Book Pages
    1. You have free access to this content
      The Nozoe Autograph Books: Segment 9

      Version of Record online: 26 FEB 2014 | DOI: 10.1002/tcr.201400107

SEARCH

SEARCH BY CITATION