Development of oxoammonium-salt-type catalysts for highly enantioselective oxidation of alcohols

• Project/Area Number: 21390001
• Research Category: Grant-in-Aid for Scientific Research (B)
• Allocation Type: Single-year Grants
• Section: 一般
• Research Field: Chemical pharmacy
• Research Institution: Tohoku University
• Principal Investigator: IWABUCHI Yoshiharu 東北大学, 大学院・薬学研究科, 教授 (20211766)
• Co-Investigator(Kenkyū-buntansha): SHIBUYA Masatoshi 東北大学, 大学院・薬学研究科, 助教 (40359534) ; 福田 隼 東北大学, 大学院・薬学研究科, 助手 (30434450)
• Project Period (FY): 2009 – 2011
• Project Status: Completed (Fiscal Year 2011)
• Budget Amount: ¥18,460,000 (Direct Cost: ¥14,200,000、Indirect Cost: ¥4,260,000); Fiscal Year 2011: ¥3,120,000 (Direct Cost: ¥2,400,000、Indirect Cost: ¥720,000); Fiscal Year 2010: ¥4,420,000 (Direct Cost: ¥3,400,000、Indirect Cost: ¥1,020,000); Fiscal Year 2009: ¥10,920,000 (Direct Cost: ¥8,400,000、Indirect Cost: ¥2,520,000)
• Keywords: 有機触媒 / 酸化反応 / オキソアンモニウム塩 / ニトロキシド / 不斉反応 / アザアダマンタン / 不斉酸化 / アルコール酸化 / 不斉触媒 / 分子認識 / ニトロキシルラジカル

Research Abstract

We have developed organocatalytic highly enatiolselecitve oxidation of alcohols based on chiral modifications of 2-azaadamantane N-oxy (AZADO)-derived oxoammonium salts. The chiral AZADOs enabled a highly enantioselecitive kinetic oxidation of racemic secondary alcohols with a broad substrate applicability.

Research Products

• [Journal Article] Oxidation of Alcohols to Carbonyl Compounds with Diisopropyl Azodicarboxylate Catalyzed by Nitroxyl Radicals (2012)
  • Author(s): M. Hayashi, M. Shibuya, Y. Iwabuchi
  • Journal Title: J. Org. Chem Volume: 77 Issue: 6 Pages: 3005-3009
  • DOI: 10.1021/jo300088b
  • Peer Reviewed
• [Journal Article] Practical Preparation Methods for Highly Active Azaadamantane-Nitroxyl-Radical-Type Oxidation Catalysts (2011)
  • Author(s): M. Shibuya, Y. Sasano, M. Tomizawa, T. Hamada, M. Kozawa, N. Nagahama, Y. Iwabuchi
  • Journal Title: Synthesis Volume: 2011 Issue: 21 Pages: 1570-1573
  • DOI: 10.1055/s-0030-1260257
  • Peer Reviewed
• [Journal Article] 9-Azanoradamantane N-Oxyl (Nor-AZADO): A Highly Active Organocatalyst for Alcohol Oxidation (2011)
  • Author(s): M. Hayashi, Y. Sasano, S. Nagasawa, M. Shibuya, Y. Iwabuchi
  • Journal Title: Chemical and Pharmaceutical Bulletin Volume: 59 Issue: 12 Pages: 1570-1573
  • DOI: 10.1248/cpb.59.1570
  • NAID: 130001852136
  • ISSN: 0009-2363, 1347-5223
  • Peer Reviewed
• [Journal Article] Highly Efficient, Organocatalytic Aerobic Alcohol Oxidation (2011)
  • Author(s): M. Shibuya, Y. Osada, Y. Sasano, M. Tomizawa, Y. Iwabuchi
  • Journal Title: J. Am. Chem. Soc Volume: 133 Issue: 17 Pages: 6497-6500
  • DOI: 10.1021/ja110940c
  • Peer Reviewed
• [Journal Article] 9-Azanoradamantane N-oxyl (NOr-AZADO) : a highly active organocatalyst for alcohol (2011)
  • Author(s): M.Hayashi, Y.Sasano, S.Nagasawa, M.Shibuya, Y.Iwabuchi
  • Journal Title: Chem.Pharm.Bull. Volume: 59 Pages: 1570-1573
  • Peer Reviewed
• [Journal Article] Highly Efficient, Organocatalytic Aerobic Alcohol Oxidation (2011)
  • Author(s): M.Shibuya, Y.Osada, Y.Sasano, M.Tomizawa, Y.Iwabuchi
  • Journal Title: J.Am.Chem.Soc. Volume: 133 Pages: 6497-6500
  • Peer Reviewed
• [Journal Article] Total synthesis and determination of the absolute configuration of (-)-idesolide (2010)
  • Author(s): H. Yamakoshi, M. Shibuya, M. Tomizawa, Y. Osada, N. Kanoh, Y. Iwabuchi
  • Journal Title: Org. Lett Volume: 12 Issue: 5 Pages: 980-983
  • DOI: 10.1021/ol9029676
  • Peer Reviewed
• [Journal Article] Total synthesis and determination of the absolute configuration of (-)-idesolide (2010)
  • Author(s): H.Yamakoshi, M.Shibuya, M.Tomizawa, Y.Osada, N.Kanoh, Y.Iwabuchi
  • Journal Title: Organic Letters 12 Pages: 980-983
  • Peer Reviewed
• [Journal Article] Highly Enantioselective Oeganocatalytic Oxidative Kinetic Resolution of Secondary Alcohols Using Chirally Modified AZADOs (2009)
  • Author(s): M. Tomizawa, M. Shibuya, Y. Iwabuchi
  • Journal Title: Org. Lett Volume: 11 Issue: 8 Pages: 1829-1831
  • DOI: 10.1021/ol900441f
  • Peer Reviewed
• [Presentation] 高活性アルコール酸化触媒AZADOの発見と展開 (2012)
  • Author(s): 岩渕好治
  • Organizer: 日本薬学会第132年会
  • Place of Presentation: 北海道大学
  • Year and Date: 2012-03-29
• [Presentation] 高活性アルコール酸化触媒AZADOの発見と展開 (2012)
  • Author(s): 岩渕好治
  • Organizer: 日本薬学会第132年会
  • Place of Presentation: 北海道大学(招待講演)
  • Year and Date: 2012-03-29
• [Presentation] キラルAZADO誘導体を触媒とするラセミ第2級アルコールの酸化的速度論的工学分割法の開発と応用 (2011)
  • Author(s): 村上景一、富澤正樹、笹野裕介、澁谷正俊、岩渕好治
  • Organizer: 第41回複素環化学討論会
  • Place of Presentation: 崇城大学市民ホール(熊本)
  • Year and Date: 2011-10-20
• [Presentation] Enantioselective Oxidative Kinetic Resolution of Racemic Secondary Alcohols using Chirally Modified AZADOs (2011)
  • Author(s): Y. Iwabuchi
  • Organizer: First Germany-Japan Organocatalytic Symposium
  • Place of Presentation: 京都大学
  • Year and Date: 2011-10-15
• [Presentation] Enantioselective Oxidative Kinetic Resolution of Racemic Secondary Alcohols using Chirally Modified AZADOs (2011)
  • Author(s): Yoshiharu Iwabuchi
  • Organizer: First Germany Japan Organocatalytic Symposium
  • Place of Presentation: 京都大学(招待講演)
  • Year and Date: 2011-10-15
• [Presentation] En Route to Molecular Complex Systems for Efficient Aerobic Oxidation of Alcohols (2010)
  • Author(s): Y. Iwabuchi
  • Organizer: 2010 International Chemical Congress of Pacific Basin Societies
  • Place of Presentation: Honolulu, USA
  • Year and Date: 2010-12-19
• [Presentation] Enantioselective Oxidative Kinetic Resolution of Racemic Secondary Alcohols Using Chirally Modified AZADOs (2010)
  • Author(s): Y. Iwabuchi
  • Organizer: 2010 International Chemical Congress of Pacific Basin Societies
  • Place of Presentation: Honolulu, USA
  • Year and Date: 2010-12-17
• [Presentation] Enantioselective Oxidative Kinetic Resolution of Racemic Secondary Alcohols Using Chirally Modified AZADOs. (2010)
  • Author(s): Y.Iwabuchi
  • Organizer: 2010 International Chemical Congress of Pacific Basin Societies
  • Place of Presentation: Honolulu, USA
  • Year and Date: 2010-12-17
• [Presentation] Aerobic Oxidation of Alcohols using Nitroxyl Radical Catalysts (2010)
  • Author(s): M.Shibuya
  • Organizer: 2010 International Chemical Congress of Pacific Basin Societies
  • Place of Presentation: Honolulu, USA
  • Year and Date: 2010-12-16
• [Presentation] Organocatalytic oxidative kinetic resolution of racemic secondary alcohols (2009)
  • Author(s): Y. Iwabuchi
  • Organizer: The International Start-up Conference of Cutting-Edge Organic Chemistry in Asia (II)
  • Place of Presentation: 千葉大学
  • Year and Date: 2009-08-11
• [Presentation] Organocatalytic oxidative kinetic resolution of racemic secondary alcohols (2009)
  • Author(s): Y.Iwabuchi
  • Organizer: The International Start-up Conference of Cutting-Edge Organic Chemistry in Asia(II)
  • Place of Presentation: 千葉大学
  • Year and Date: 2009-08-11
• [Remarks]
  • URL: http://www.pharm.tohoku.ac.jp/~gousei/synthetic/index.html