感応性化学種による触媒反応の制御・設計に関する理論的研究

• Project Area: Stimuli-responsive Chemical Species for the Creation of Functional Molecules
• Project/Area Number: 25109525
• 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, シニアリサーチフェロー (40111083)
• Project Period (FY): 2013-04-01 – 2015-03-31
• Project Status: Completed (Fiscal Year 2014)
• Budget Amount: ¥7,540,000 (Direct Cost: ¥5,800,000、Indirect Cost: ¥1,740,000); Fiscal Year 2014: ¥3,770,000 (Direct Cost: ¥2,900,000、Indirect Cost: ¥870,000); Fiscal Year 2013: ¥3,770,000 (Direct Cost: ¥2,900,000、Indirect Cost: ¥870,000)
• Keywords: 感応性化学種 / 計算化学 / 遷移金属錯体 / テルペン類 / 均一系触媒 / 反応経路探索 / 感応性分子種 / ランタニド錯体 / 向山アルドール反応 / 芳香族性

Outline of Annual Research Achievements

我々が開発した反応経路自動検索法を、本新学術領域の主テーマである感応性化学種の新物質科学に応用して、感応性化学種の構造、反応性、さらに触媒反応の機構、選択性の起源を理論的に明らかにする。
1.化学反応径路自動探索(GRRM)戦術の感応性化学種の化学反応への応用　a. セスキテルペン類生成および異性化経路を明らかにするため、既知のプロトン化カチオンのからの異性化経路を自動探索法AFIR法を用いて探索し、従来見いだされている経路およびセスキテルペン異性体の他に、全く知られていなかった経路をいくつか見いだした (Isegawa et al., Chem. Sci. 5, 1555-1560 (2014))。　　b. AFIR法を用いた不斉遷移金触媒反応機構の解明: 銅錯体とDNAとの超分子錯体を触媒とする不斉フリーデルクラフツ反応のエナンチオ選択性の起源を、AFIR法による反応経路の自動検索をもとに明らかにした(Petrova et al., Chem. Phys. Lett. 600, 87-95 (2014)。　c. AFIR法を用いた有機分子触媒反応機構の解明 (Petrova et al., J. Phys. Chem. B, 118, 5154-5167 (2014); Moteki et al., Chem. Asian J. 印刷中) 。
2. Rh錯体触媒によるベンゾシクロブテノールのCsp3-Csp2結合とCsp3-Csp3結合の選択的解裂の起源を明らかにした (Ding et al., J. Am. Chem. Soc. 136, 169-178 (2014).
3. ONIOM法に関する印刷120頁、引用文献800件に上る網羅的な総説を完成し, 発表した。Chung et al., Chem. Rev. 印刷中

Research Progress Status

26年度が最終年度であるため、記入しない。

Strategy for Future Research Activity

26年度が最終年度であるため、記入しない。

Research Products

• [Journal Article] The ONOIM Method and its Applications (2015)
  • Author(s): L. W. Chung, W. M. C. Sameera, R. Ramozzi, A. J. Page, M. Hatanaka, G. P. Petrova, T. V. Harris, X. Li, Z. Ke, F. Liu, H.-B. Li, L. Ding, and K. Morokuma
  • Journal Title: Chem. Rev. Volume: 115 Issue: 12 Pages: 1-119
  • DOI: 10.1021/cr5004419
  • Peer Reviewed / Open Access / Acknowledgement Compliant
• [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] sp3-sp2 vs sp3-sp3 C-C Site-Selectivity in Rh-Catalyzed Ring Opening of Benzocyclobutenol: A DFT Study (2014)
  • Author(s): Lina Ding, Naoki Ishida, Masahiro Murakami, and Keiji Morokuma
  • Journal Title: Journal of the American Chemical Society Volume: 136 Issue: 1 Pages: 169-178
  • DOI: 10.1021/ja407422q
  • Peer Reviewed
• [Journal Article] Excited-State Proton Transfer Controls Irreversibility of Photoisomerization in Mononuclear Ruthenium(II) Monoaquo Complexes: A DFT Study (2014)
  • Author(s): L. Ding, L. W. Chung, and K. Morokuma
  • Journal Title: J. Chem. Theo. Comp. Volume: 10 Issue: 2 Pages: 668-675
  • DOI: 10.1021/ct400982r
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Predicting pathways for terpene formation from first principles - routes to known and new sesquiterpenes (2014)
  • Author(s): Miho Isegawa, Satoshi Maeda, Dean J. Tantillo, and Keiji Morokuma
  • Journal Title: Chemical Science Volume: 5 Issue: 4 Pages: 1555-1560
  • DOI: 10.1039/c3sc53293c
  • Peer Reviewed
• [Journal Article] The origin of enantioselectivity for intramolecular Friedel-Crafts reaction catalyzed the supramolecular Cu / DNA catalyst complex (2014)
  • Author(s): G. P. Petrova, Z. Ke, S. Park, H. Sugiyama and K. Morokuma
  • Journal Title: Chem. Phys. Lett. Volume: 600 Pages: 87-95
  • DOI: 10.1016/j.cplett.2014.03.060
  • NAID: 120005439185
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Asymmetric phase-transfer catalysis with homo- and heterochiral quaternary ammonium salts: a theoretical study (2014)
  • Author(s): G. P. Petrova, H.-B. Li, K. Maruoka and K. Morokuma,
  • Journal Title: J. Phys. Chem. Volume: 118 Issue: 19 Pages: 5154-5167
  • DOI: 10.1021/jp501520g
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] σ-Aromaticity in Hexa-Group 16 Atom-Substituted Benzene Dications. A Theoretical Study (2014)
  • Author(s): Miho Hatanaka, Masaichi Saito, Masahiro Fujita, and Keiji Morokuma
  • Journal Title: The Journal of Organic Chemistry Volume: 79 Issue: 6 Pages: 2640-2646
  • DOI: 10.1021/jo500098h
  • Peer Reviewed
• [Journal Article] Theoretical Study of Mukaiyama-Aldol Reaction Catalyzed by Water-Tolerant Lanthanide Lewis Acid (2013)
  • Author(s): M. Hatanaka, K. Morokuma,
  • Journal Title: J. Am. Chem. Soc. Volume: 135 Issue: 37 Pages: 1397213979-1397213979
  • DOI: 10.1021/ja407357c
  • Peer Reviewed
• [Presentation] 20.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
• [Presentation] 19.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
• [Presentation] 18.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
• [Presentation] 17.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
• [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
• [Presentation] Theory and Computation Provide Insights and Discovery on Chemical Reactions of Complex Molecular Systems (2014)
  • Author(s): Keiji Morokuma
  • Organizer: Advanced Molecular Transformations by Organocatalysts, 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] heory 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] 11.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 Application (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
• [Presentation] Chemical Theory of Complex Molecular Systems: Discovery and Insights from Computational Studies of Chemical Reactions (2014)
  • Author(s): 諸熊奎治
  • Organizer: CRC‐EC Joint International Symposium on Chemical Theory for Complex Systems
  • Place of Presentation: Atlanta, GA, USA
  • Invited
• [Presentation] Exploring potential energy surfaces with GRRM automatic search strategy (2013)
  • Author(s): 諸熊奎治
  • Organizer: International Symposium on Organic Reaction Mechanism
  • Place of Presentation: Shenzhen, China
  • Invited
• [Presentation] Development of Advanced Approaches to Potential Energy Landscaping for Fuel Cracking and Oxidation (2013)
  • Author(s): 諸熊奎治
  • Organizer: US AFOSR symposium on combustion
  • Place of Presentation: Arlington, VA, USA
  • Invited
• [Presentation] Exciting World of Theoretical Studies of Chemical Reactions -- From Gas Phase Reactions to Catalysts, and Enzymatic Reactions (2013)
  • Author(s): 諸熊奎治
  • Organizer: Asian Pacific Conference of Theoretical and Computational Chemistry (APCTCC6)
  • Place of Presentation: Gyeonju, Korera
  • Invited
• [Presentation] Theory Can Provide Insights Unavailable from Experiments in Catalysis (2013)
  • Author(s): 諸熊奎治
  • Organizer: The Sixteenth International Symposium on Relations between Homogeneous and Heterogeneous Catalysis
  • Place of Presentation: Sapporo, Japan
  • Invited
• [Presentation] Automatic exploration of potential energy surfaces for catalysis and other complex chemical reactions (2013)
  • Author(s): 諸熊奎治
  • Organizer: DOE Symposium on New Theoretical Concepts and Directions in Catalysis
  • Place of Presentation: Santa Barbara, CA, USA
  • Invited
• [Presentation] Exciting World of Theoretical/Computational Studies of Chemical Reactions of Complex Chemical Systems (2013)
  • Author(s): 諸熊奎治
  • Organizer: CMSI International Symposium “Extending the power of computational materials sciences with K-computer”
  • Place of Presentation: Tokyo, Japan
  • Invited
• [Presentation] Automatic exploration of reaction pathways in complex environments, Symposium on "Electronic Structure in Complex Environments (2013)
  • Author(s): 諸熊奎治
  • Organizer: Southeast Regional Meeting of the American Chemical Society
  • Place of Presentation: Atlanta, GA, USA
  • Invited
• [Presentation] Complex Chemical Reaction Pathways Explored by Automatic Search Strategy (2013)
  • Author(s): 諸熊奎治
  • Organizer: 5th Japan-Czech-Slovakia International Symposium on Theoretical Chemistry
  • Place of Presentation: Nara, Japan
  • Invited
• [Presentation] 反応経路自動探索法などを用いた化学反応の理論
  • Author(s): 諸熊奎治
  • Organizer: 企業研究会 CAMMフォーラム
  • Place of Presentation: 東京
  • 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] 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