Computational Analyses for extremely difficult substrate conversion reactions

• Project Area: Precise Formation of a Catalyst Having a Specified Field for Use in Extremely Difficult Substrate Conversion Reactions
• Project/Area Number: 18H04233
• Research Category: Grant-in-Aid for Scientific Research on Innovative Areas (Research in a proposed research area)
• Allocation Type: Single-year Grants
• Research Institution: Ibaraki University
• Principal Investigator: 森 聖治 茨城大学, 理工学研究科(理学野), 教授 (50332549)
• Project Period (FY): 2018-04-01 – 2020-03-31
• Project Status: Completed (Fiscal Year 2019)
• Budget Amount: ¥6,240,000 (Direct Cost: ¥4,800,000、Indirect Cost: ¥1,440,000); Fiscal Year 2019: ¥3,120,000 (Direct Cost: ¥2,400,000、Indirect Cost: ¥720,000); Fiscal Year 2018: ¥3,120,000 (Direct Cost: ¥2,400,000、Indirect Cost: ¥720,000)
• Keywords: 量子化学計算 / 金属触媒 / 反応機構 / 高エナンチオ選択性 / 非共有結合性相互作用 / C-H結合活性化 / C-C結合活性化 / 電子状態 / C-O結合活性化 / 環化反応

Outline of Annual Research Achievements

令和元年度は以下の研究を行い、令和２年度にかけて学術誌論文に報告した。
(1) 計画班員である北海道大学の澤村教授と共同で、イリジウムと窒素およびリン配位子を含む不斉プロリノールーホスフィン誘導体との協同触媒によるケトンのエナンチオ選択的還元反応を報告した。この研究では、t-ブチルフェニルケトンのような、かさ高いケトンでも高立体選択的( >99 %ee)に反応が進行することが明らかになったほか、エナンチオ選択性の説明に、プロリノールーホスフィン誘導体のC-H・・O相互作用やピロリジン環のC-H結合および基質のフェニル基とのC-H/π相互作用など非共有結合性相互作用が重要であることを、DFT計算（B3LYP+D3(BJ)-PCM/def2TZVPP//B3LYP+D3(BJ)/def2SVPレベル）およびそれらの電子密度解析によっても明らかにした。
(2) 国際共同研究
昆虫病原糸状菌から単離されたorbiochromone Aおよび木材腐朽担子菌Ganodermaから単離されたganocolossusin AおよびDの電子円二色性スペクトルと、TD-DFT計算の結果と比較して、その絶対立体配置を決めることができた。タイ・BIOTECの伊坂雅彦博士との共同研究で示した。さらに、バナジウム-N-サリチリデン型配位子協奏触媒によるオレフィンの1,2-酸化的トリフルオロメチル化反応を、台湾国立清華大学のChen教授らと報告し、触媒の空気酸化の後に起こる1,5-水素移動の段階でバナジウムのアピカル位に結合しているオキソ配位子が基質の水素を引き抜いていることが実験とDFT計算によって示唆された。

Research Progress Status

令和元年度が最終年度であるため、記入しない。

Strategy for Future Research Activity

令和元年度が最終年度であるため、記入しない。

Research Products

• [Int'l Joint Research] チェンマイ大学/ウボン・ラーチャーターニー大学/BIOTEC(タイ)
• [Int'l Joint Research] 台湾国立清華大学(その他の国・地域)
• [Journal Article] Vanadyl Species Catalyzed 1,2-Oxidative Trifluoromethylation of Unactivated Olefins (2020)
  • Author(s): Chen Chien-Tien、Chen Ya-Pei、Tsai Bang-You、Liao Yi-Ya、Su Yu-Cheng、Chen Tsung-Cheng、Lu Chia-Hao、Fujii Ryoma、Kawashima Kyohei、Mori Seiji
  • Journal Title: ACS Catalysis Volume: 10 Issue: 6 Pages: 3676-3683
  • DOI: 10.1021/acscatal.0c00370
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Iridium‐Catalyzed Enantioselective Transfer Hydrogenation of Ketones Controlled by Alcohol Hydrogen‐Bonding and sp 3 ‐C?H Noncovalent Interactions (2020)
  • Author(s): Murayama Hiroaki、Heike Yoshito、Higashida Kosuke、Shimizu Yohei、Yodsin Nuttapon、Wongnongwa Yutthana、Jungsuttiwong Siriporn、Mori Seiji、Sawamura Masaya
  • Journal Title: Advanced Synthesis & Catalysis Volume: 362 Issue: 21 Pages: 4655-4661
  • DOI: 10.1002/adsc.202000615
  • NAID: 120007168181
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Highly Modified Lanostane Triterpenes from the Wood-Rot Basidiomycete Ganoderma colossus: Comparative Chemical Investigations of Natural and Artificially Cultivated Fruiting Bodies and Mycelial Cultures (2020)
  • Author(s): Isaka Masahiko、Chinthanom Panida、Choeyklin Rattaket、Thummarukcharoen Tuksaporn、Rachtawee Pranee、Sappan Malipan、Srichomthong Kitlada、Fujii Ryoma、Kawashima Kyohei、Mori Seiji
  • Journal Title: Journal of Natural Products Volume: 83 Issue: 7 Pages: 2066-2075
  • DOI: 10.1021/acs.jnatprod.9b00947
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Benzophenone and chromone derivatives and their dimers from the scale-insect pathogenic fungus Orbiocrella petchii BCC 51377 (2019)
  • Author(s): Isaka Masahiko、Palasarn Somporn、Choowong Wilunda、Kawashima Kyohei、Mori Seiji、Mongkolsamrit Suchada、Thanakitpipattana Donnaya
  • Journal Title: Tetrahedron Volume: 75 Issue: 45 Pages: 130646-130646
  • DOI: 10.1016/j.tet.2019.130646
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Cavity Closure of 2-Hydroxypropyl-β-Cyclodextrin: Replica Exchange Molecular Dynamics Simulations (2019)
  • Author(s): Kerdpol Khanittha、Kicuntod Jintawee、Wolschann Peter、Mori Seiji、Rungnim Chompoonut、Kunaseth Manaschai、Okumura Hisashi、Kungwan Nawee、Rungrotmongkol Thanyada
  • Journal Title: Polymers Volume: 11 Issue: 1 Pages: 145-145
  • DOI: 10.3390/polym11010145
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Theoretical Investigations of Rh-Catalyzed Asymmetric 1,4-Addition to Enones using Planar-Chiral Phosphine-Olefin Ligands (2019)
  • Author(s): Kawashima, K.; Sato, T.; Ogasawara, M.; Kamikawa, K.; Mori, S.
  • Journal Title: J. Comput. Chem. Volume: 40 Issue: 1 Pages: 113-118
  • DOI: 10.1002/jcc.25550
  • Peer Reviewed
• [Journal Article] Computational Modelling Study on the Pseudoazurin Type?1 Cu Site (2019)
  • Author(s): Taborosi Attila、Yamaguchi Takahide、Mori Seiji、Kohzuma Takamitsu
  • Journal Title: JPS Conference Proceeding Volume: 25 Pages: 01106-01106
  • DOI: 10.7566/jpscp.25.011006
  • Peer Reviewed / Open Access
• [Journal Article] Recent Advances for Reaction Mechanisms of Metal-Catalyzed Activations of Carbon-Containing Bonds with the Aid of Density Functional Calculations (2018)
  • Author(s): Mori Seiji
  • Journal Title: Bulletin of Japan Society of Coordination Chemistry Volume: 72 Issue: 0 Pages: 15-29
  • DOI: 10.4019/bjscc.72.15
  • NAID: 130007622303
  • ISSN: 1882-6954, 1883-1737
  • Year and Date: 2018-11-30
  • Peer Reviewed / Open Access
• [Journal Article] Enantiocontrol by assembled attractive interactions in copper-catalyzed asymmetric direct alkynylation of α-ketoesters with terminal alkynes: OH-O/sp3-CH-O two-point hydrogen bonding combined with dispersive attractions (2018)
  • Author(s): Schwarzer Martin C.、Fujioka Akane、Ishii Takaoki、Ohmiya Hirohisa、Mori Seiji、Sawamura Masaya
  • Journal Title: Chemical Science Volume: 9 Issue: 14 Pages: 3484-3493
  • DOI: 10.1039/c8sc00527c
  • Peer Reviewed / Open Access
• [Journal Article] QM/MM Investigation for Protonation States in a Bilin Reductase PcyA-Biliverdin IXalpha Complex (2018)
  • Author(s): Eri Iijima, Matthew Paul Gleeson, Masaki Unno, Seiji Mori
  • Journal Title: ChemPhysChem Volume: 印刷中 Issue: 15 Pages: 1809-1813
  • DOI: 10.1002/cphc.201800031
  • Peer Reviewed / Int'l Joint Research
• [Presentation] Pd触媒による2-アルキルピリジン類の側鎖C(α)位のエナンチオ選択的直接アリル化反応に関する理論的研究 (2020)
  • Author(s): 川島恭平、山本春奈、村上遼、佐野建太郎、岩井智弘、澤村正也、森聖治
  • Organizer: 化学反応経路探索のニューフロンティア2020
• [Presentation] バナジウム触媒によるオレフィンの1,2-酸化的トリフルオロメチル化反応における実験的・理論的研究 (2020)
  • Author(s): 藤井 稜馬・川島 恭平・森 聖治・Su Yu-Cheng・Lu Chia-Hao・Lien Chien-I・Sagar Ramu・Chen Chien-Tien
  • Organizer: 第10回CSJ化学フェスタ2020
• [Presentation] Computational Insights into Structures and Reactions of Homogeneous and Enzymatic Catalysts (2019)
  • Author(s): Seiji Mori
  • Organizer: The Organic & Biomolecular Chemistry conference
  • Int'l Joint Research / Invited
• [Presentation] DFT Investigations of Oxidative Kinetic Resolution of Racemic Secondary Alcohols Using Chiral Ligand-Hybridized Nitroxyl Radical/Copper Cooperative Catalysis (2019)
  • Author(s): Kyohei Kawashima, Seiji Mori
  • Organizer: 2nd ICReDD International Symposium-Toward Interdisciplinary Research Guided by Theory and Calculation
  • Int'l Joint Research
• [Presentation] DFT Investigations of Oxidative Kinetic Resolution of Racemic Secondary Alcohols Using Chiral Ligand-Hybridized Nitroxyl Radical/Copper Cooperative Catalysis (2019)
  • Author(s): 川島 恭平, 笹野 裕介, 小暮 直貴, 笠畑 洸希, 岩渕 好治, 森 聖治
  • Organizer: 錯体化学会第６９回討論会
• [Presentation] Bridges between experiment and theory on catalytic functions (2019)
  • Author(s): Seiji Mori
  • Organizer: 1st IUPAP Conference on Computational Physics (CCP2019)
  • Int'l Joint Research / Invited
• [Presentation] Mechanistic Insights into Metal-Catalyzed Highly Selective Homogeneous Organic Transformation Reactions (2019)
  • Author(s): Seiji Mori
  • Organizer: The 10th International Conference of the Asian Consortium on Computational Materials Science (ACCMS-10)
  • Int'l Joint Research / Invited
• [Presentation] ビリン還元酵素PcyAが触媒するビリベルジンIX?の還元反応に関するONIOM法を用いた研究 (2019)
  • Author(s): 三ツ泉 宏晃・飯島 愛璃・海野 昌喜・M. Paul Gleeson・森 聖治
  • Organizer: 日本化学会第99春季年会
• [Presentation] 不斉配位子複合型ニトロキシルラジカル/銅協同触媒を用いるラセミ第2級アルコールの酸化的速度論的光学分割に関する理論的研究 (2019)
  • Author(s): 川島 恭平・笹野 裕介・笠畑 洸希・岩渕 好治・森 聖治
  • Organizer: 日本化学会第99春季年会
• [Presentation] Mechanistic Insights into Metal-Catalyzed Highly Selective Organic Transformation Reactions (2018)
  • Author(s): Seiji Mori
  • Organizer: The 28th Canadian Symposium on Theoretical and Computational Chemistry
  • Int'l Joint Research / Invited
• [Presentation] Mechanistic Insights into Metal Catalyzed Highly Selective Organic Transformation Reactions (2018)
  • Author(s): Seiji Mori
  • Organizer: 22nd International Annual Symposium on Computational Science and Engineering
  • Int'l Joint Research / Invited
• [Presentation] Bridges Between Experiment And Theory On Catalytic Functions (2018)
  • Author(s): Seiji Mori
  • Organizer: Computer Aided Drug Design (CADD) 2018 Seminar and Workshop
  • Int'l Joint Research / Invited
• [Presentation] 不斉配位子複合型ニトロキシルラジカル/銅協同触媒を用いる ラセミ第2級アルコールの酸化的速度論的光学分割に関する理論的研究 (2018)
  • Author(s): 川島 恭平・笹野 裕介・小暮 直貴・笠畑 洸希・岩渕 好治・森 聖治
  • Organizer: 第12回分子科学討論会2018福岡
• [Remarks] 物理有機化学研究室ホームページ
  • URL: http://smori.sci.ibaraki.ac.jp/
• [Remarks] 茨城大学研究者情報総覧
  • URL: https://info.ibaraki.ac.jp/Profiles/5/0000478/profile.html
• [Remarks] 物理有機化学研究室ホームページ