反応経路自動探索法による有機分子触媒反応機構の解明と設計

• Project Area: Advanced Molecular Transformations by Organocatalysts
• Project/Area Number: 26105733
• Research Category: Grant-in-Aid for Scientific Research on Innovative Areas (Research in a proposed research area)
• Allocation Type: Single-year Grants
• Review Section: Science and Engineering
• Research Institution: Kyoto University
• Principal Investigator: 諸熊 奎治 京都大学, 福井謙一記念研究センター, FIFCリサーチフェロー (40111083)
• Project Period (FY): 2014-04-01 – 2016-03-31
• Project Status: Completed (Fiscal Year 2015)
• Budget Amount: ¥6,760,000 (Direct Cost: ¥5,200,000、Indirect Cost: ¥1,560,000); Fiscal Year 2015: ¥3,380,000 (Direct Cost: ¥2,600,000、Indirect Cost: ¥780,000); Fiscal Year 2014: ¥3,380,000 (Direct Cost: ¥2,600,000、Indirect Cost: ¥780,000)
• Keywords: 有機分子触媒 / 触媒反応 / 理論的研究 / 相関移動触媒反応 / 反応経路自動探索法 / 計算化学 / 均一系触媒 / 反応経路探索 / 多成分有機反応 / カウンター陰イオン指向触媒 / 溶媒効果

Outline of Annual Research Achievements

1)不斉カウンターアニオン指向触媒（ACDC）の反応機構と制御
ACDCを用いた立体選択的細見桜井反応は多成分反応であり、反応機構の全容を知るためには、どのような順番で反応が起こるのかを解析する必要がある。AFIR法を活用して複数の反応経路をもとめ、立体選択性の起源を調べた。立体選択性の起源はプレ触媒とシリルケテンアセタールの錯形成にあることがわかった。

2)分岐アルデヒドのC-H結合の無金属活性化の反応機構
超原子価ヨウ素化合物を用いたアルデヒドのCH結合活性化の機構を検討した。まず、光照射によりカルボキシラジカルが生成し、このカルボキシラジカルがアルデヒドのCH結合を切断することがわかった。生成したラジカルによる連鎖反応によりアシル化反応が進行する。

Research Progress Status

27年度が最終年度であるため、記入しない。

Strategy for Future Research Activity

27年度が最終年度であるため、記入しない。

Research Products

• [Journal Article] Computational Catalysis Using the Artificial Force Induced Reaction Method (2016)
  • Author(s): W. M. C. Sameera, Satoshi Maeda and Keiji Morokuma
  • Journal Title: Acc. Chem. Res. Volume: 49 Issue: 4 Pages: 763773-763773
  • DOI: 10.1021/acs.accounts.6b00023
  • Peer Reviewed
• [Journal Article] How Can Fluctional Chiral Lanthanide (III) Complexes Achieve a High Stereoselectivity in Aqueous Mukaiyama-Aldol Reaction? (2015)
  • Author(s): M. Hatanaka, K. Morokuma
  • Journal Title: ACS Catal. Volume: 5 Issue: 6 Pages: 3731-3739
  • DOI: 10.1021/acscatal.5b00438
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] The Biginelli reaction is a urea-catalyzed organocatalytic multicomponent reaction (2015)
  • Author(s): M. Puripat, R. Ramozzi, M. Hatanaka, W. Parasuk, V. Parasuk, K. Morokuma
  • Journal Title: J. Org. Chem. Volume: 80 Issue: 14 Pages: 6959-6967
  • DOI: 10.1021/acs.joc.5b00407
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Revisiting the Passerini Reaction Mechanism: Existence of the Nitrilium, Organocatalysis of Its Formation, and Solvent Effect (2015)
  • Author(s): Romain Ramozzi and Keiji Morokuma
  • Journal Title: J. Org. Chem. Volume: 80 Issue: 11 Pages: 56525657-56525657
  • DOI: 10.1021/acs.joc.5b00594
  • Peer Reviewed
• [Journal Article] Positive Effect of Water in Asymmetric Direct Aldol Reactions with Primary-Amine Organocatalyst: Experimental and Computational Studies (2015)
  • Author(s): S A. Moteki, K. Nakayama, H.-B. Li, G. Petrova, S. Maeda, K. Morokuma, and K. Maruoka
  • Journal Title: Chem. Asian J. Volume: 10 Issue: 10 Pages: 1-6
  • DOI: 10.1002/asia.201500078
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Revisiting the Passerini reaction mechanism: existence of the nitrilium, organocatalysis of its formation and solvent effect (2015)
  • Author(s): R. Ramozzi, K. Morokuma
  • Journal Title: J. Org. Chem. Volume: 80 Pages: 1-6
  • Peer Reviewed / Acknowledgement Compliant
• [Presentation] Automatic exploration of crossings of potential energy surfaces for photochemical and excited state reactions (2015)
  • Author(s): 諸熊 奎治
  • Organizer: 分子衝突動力学国際会議
  • Place of Presentation: モンテレー、アメリカ合衆国
  • Year and Date: 2015-07-12
  • Int'l Joint Research / Invited
• [Presentation] Gas-Phase Photochemical and Homogenous Catalytic Reactions Explored Using the Automated Reaction Route Mapping (GRRM) Method (2015)
  • Author(s): Keiji Morokuma
  • Organizer: American Chemical Society Semi-annual Meeting
  • Place of Presentation: Denver, USA
  • Year and Date: 2015-03-23
  • Invited
• [Presentation] Exciting World of Theoretical Studies of Chemical Reactions － From Gas Phase Reactions to Catalysts, and Enzymatic Reactions (2015)
  • Author(s): Keiji Morokuma
  • Organizer: Argonne National Laboratory
  • Place of Presentation: Argonne, USA
  • Year and Date: 2015-03-17
  • Invited
• [Presentation] Chemical Reactions of Complex Molecular Systems -- Discovery and Insights from Computational Studies, (2015)
  • Author(s): Keiji Morokuma
  • Organizer: 12th Fukui Institute Symposium,
  • Place of Presentation: 京都
  • Year and Date: 2015-01-23
  • Invited
• [Presentation] Fascinating World of Theoretical Studies of Chemical Reaction--From Gas Phase Reactions to Catalysts, and Enzymatic Reactions (2014)
  • Author(s): Keiji Morokuma
  • Organizer: Hiroshima University
  • Place of Presentation: 広島
  • Year and Date: 2014-12-03
  • Invited
• [Presentation] GRRM法を用いた複雑分子系の反応機構 (2014)
  • Author(s): 諸熊 奎治
  • Organizer: GRRM誕生十周年・GRRM14発表記念講演会 「GRRMで拓く化学のニューフロンティア」
  • Place of Presentation: 東京
  • Year and Date: 2014-11-30
  • Invited
• [Presentation] Theory and Computation Provide Insights and Discovery on Chemical Reactions of Complex Molecular Systems, Advanced Molecular Transformations by Organocatalysts (2014)
  • Author(s): Keiji Morokuma
  • Organizer: 2nd International Conference and 7th Symposium on Organocatalysis
  • Place of Presentation: 東京
  • Year and Date: 2014-11-21
  • Invited
• [Presentation] Chemical Theory of Complex Molecular Systems: Discovery and Insights from Computational Studies of Chemical Reactions (2014)
  • Author(s): Keiji Morokuma
  • Organizer: CRC-SU Joint International Symposium on Chemical Theory of Complex Systems: “Interplay between Theory and Experiments; New Trends in Catalysis”
  • Place of Presentation: Stockholm, Sweden
  • Year and Date: 2014-10-31
  • Invited
• [Presentation] Theory and Computation Provide Insights and Discovery on Chemical Reactions of Complex Molecular Systems (2014)
  • Author(s): Keiji Morokuma
  • Organizer: Japan-Russia Joint-Symposium on Chemical Theory for Complex Systems
  • Place of Presentation: St. Petersburg, Russia
  • Year and Date: 2014-09-19
  • Invited
• [Presentation] Theory and Computation Provide Insights and Discovery on Chemical Reactions of Complex Molecular Systems (2014)
  • Author(s): Keiji Morokuma
  • Organizer: International Conference "Molecular Complexity in Modern Chemistry” (MCMC-2014)
  • Place of Presentation: Moscow, Russia,
  • Year and Date: 2014-09-16
  • Invited
• [Presentation] Quantum chemical molecular dynamics (QM/MD) simulations of nucleation, growth and healing processes of fullerenes, carbon nanotubes and graphenes (2014)
  • Author(s): Keiji Morokuma
  • Organizer: the 17th International Symposium on Small Particles and Inorganic Clusters (ISSPIC XVII)
  • Place of Presentation: 福岡
  • Year and Date: 2014-09-07
  • Invited
• [Presentation] 複雑分子系のシミュレーション～生体分子の反応への応用とその周辺 (2014)
  • Author(s): 諸熊 奎治
  • Organizer: 情報計算化学生物学会（CBI学会）講演会
  • Place of Presentation: 東京
  • Year and Date: 2014-07-29
  • Invited
• [Presentation] Multiscale Computational Approaches And Applications in Biochemistry And Biomaterials (2014)
  • Author(s): Keiji Morokuma
  • Organizer: Annual Conference of Canadian Chemical Society
  • Place of Presentation: Vancouver, Canada
  • Year and Date: 2014-06-04
  • Invited
• [Presentation] Exciting World of Theoretical Studies of Chemical Reactions － From Gas Phase Reactions to Catalysts, and Enzymatic Reactions (2014)
  • Author(s): Keiji Morokuma
  • Organizer: Swiss Chemical Society Lecture
  • Place of Presentation: Lausanne, Switzerland,
  • Year and Date: 2014-05-23
  • Invited
• [Presentation] Complex Chemical Reaction Pathways Explored by Automatic Search Strategy, Swiss Chemical Society Lecture (2014)
  • Author(s): Keiji Morokuma
  • Organizer: Swiss Chemical Society Lecture
  • Place of Presentation: Zurich, Switzerland
  • Year and Date: 2014-05-22
  • Invited
• [Presentation] Theoretical Studies of Complex Molecular Systems. Methods and Applications (2014)
  • Author(s): Keiji Morokuma
  • Organizer: Swiss Chemical Society Lecture
  • Place of Presentation: Basel, Switzerland
  • Year and Date: 2014-05-21
  • Invited
• [Presentation] Chemical Theory of Complex Molecular Systems: Discovery and Insights from Computational Studies of Chemical Reactions (2014)
  • Author(s): Keiji Morokuma
  • Organizer: Swiss Chemical Society Lecture
  • Place of Presentation: Fribourg, Switzerland
  • Year and Date: 2014-05-20
  • Invited
• [Presentation] Exciting World of Theoretical Studies of Chemical Reactions － From Gas Phase Reactions to Catalysts, and Enzymatic Reactions (2014)
  • Author(s): Keiji Morokuma
  • Organizer: Swiss Chemical Society Lecture
  • Place of Presentation: Basel, Switzerland
  • Year and Date: 2014-05-19
  • Invited
• [Presentation] Theory and Computation Provide Insights and Discovery on Chemical Reactions of Complex Molecular Systems (2014)
  • Author(s): Keiji Morokuma
  • Organizer: 2014 AATACC Seminar
  • Place of Presentation: Canberra, Australia
  • Year and Date: 2014-05-01
  • Invited
• [Presentation] Theory and Computation Provide Insights and Discovery on Chemical Reactions of Complex Molecular Systems (2014)
  • Author(s): Keiji Morokuma
  • Organizer: 2014 AATACC Seminar
  • Place of Presentation: Sydney, Australia
  • Year and Date: 2014-04-29
  • Invited
• [Presentation] Exploring potential energy surfaces with GRRM automatic search strategy, Theory and Computation Provide Insights and Discovery on Chemical Reactions of Complex Molecular Systems (2014)
  • Author(s): Keiji Morokuma
  • Organizer: 2014 AATACC Seminar
  • Place of Presentation: New Castle, Australia
  • Year and Date: 2014-04-28
  • Invited
• [Remarks] Morokuma Group Web Page
  • URL: http://kmweb.fukui.kyoto-u.ac.jp/top/index.html
• [Remarks] 京都大学福井謙一記念研究センター
  • URL: http://www.fukui.kyoto-u.ac.jp/
• [Remarks] 京都大学福井謙一記念研究センター
  • URL: http://www.fukui.kyoto-u.ac.jp