Theoretical design of Extremely Difficult and Selective 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: 16H01001
• 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: Ibaraki University
• Principal Investigator: 森 聖治 茨城大学, 理学部, 教授 (50332549)
• Project Period (FY): 2016-04-01 – 2018-03-31
• Project Status: Completed (Fiscal Year 2017)
• Budget Amount: ¥5,980,000 (Direct Cost: ¥4,600,000、Indirect Cost: ¥1,380,000); Fiscal Year 2017: ¥2,990,000 (Direct Cost: ¥2,300,000、Indirect Cost: ¥690,000); Fiscal Year 2016: ¥2,990,000 (Direct Cost: ¥2,300,000、Indirect Cost: ¥690,000)
• Keywords: 量子化学計算 / 金属触媒 / 結合活性化反応 / 反応機構 / 反応経路探索 / グラフ理論 / 物質変換反応 / 触媒反応場 / 立体選択性

Outline of Annual Research Achievements

研究代表者らは、研究期間内で、金属触媒による分子変換反応のメカニズムを、量子化学計算を用いて検討した。
(1)Rh-BINAP触媒による水素移動反応の経路探索
メントール不斉合成のキーステップであるRh(BINAP)+錯体とN, N,3-trimethylbut-2-en-1-amineの反応経路の探索を、反応物を人工的に押しつけることにより遷移状態を予測し反応経路を見つけるAFIR（人工力誘起反応）法とONIOM法を組み合わせて行った。さらに、得られた複雑な反応経路ネットワークから、Primの決定論的アルゴリズムを用いて、そのグラフを抽出し最小全域木(minimal span tree)を求めた。各経路のエネルギーを比較したところ、会合機構に比べて解離機構が有利であることがわかった。
(2)Ni触媒によるC-O結合活性化反応の経路探索
Ni触媒によるメトキシナフタレンとフェニルボロン酸エステルとのC-O結合活性化を伴うクロスカップリング反応を開発し2008年に報告された。PCy3を配位子として加えたときの反応ではCsFが必須である。ただし、カルベン配位子ICyを用いたときには、CsFは不要である。DFT計算(BP86-D3汎関数)を行い反応機構の検討を行った。C-O結合の配位子の電子的効果を検討した。
(3) ほかにも、インドール置換のサレンCu(II)錯体の1電子酸化体の電子状態および、Cu(I)―プロリノール協同触媒存在下C-H結合活性化反応におけるエナンチオ選択性における弱い非共有結合（分散相互作用）の重要性について成果を出した。

Research Progress Status

平成29年度が最終年度であるため、記入しない。

Strategy for Future Research Activity

平成29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/カセサート大学(タイ)
• [Int'l Joint Research] 香港城市大学(中国)
• [Int'l Joint Research] 香港城市大学(中国)
• [Int'l Joint Research] Chiang Mai University/Kasetsart University/Mahidol University(Thailand)
• [Journal Article] Exploring the full catalytic cycle of rhodium(I)-BINAP-catalysed isomerisation of allylic amines: a graph theory approach for path optimisation (2017)
  • Author(s): Yoshimura Takayoshi、Maeda Satoshi、Taketsugu Tetsuya、Sawamura Masaya、Morokuma Keiji、Mori Seiji
  • Journal Title: Chemical Science Volume: 8 Issue: 6 Pages: 4475-4488
  • DOI: 10.1039/c7sc00401j
  • NAID: 120006324922
  • Peer Reviewed / Open Access
• [Journal Article] Asymmetric Synthesis of β‐Lactams through Copper‐Catalyzed Alkyne‐Nitrone Coupling with Prolinol‐Phosphine Chiral Ligand (2017)
  • Author(s): Yurie Takayama, Takaoki Ishii, Hirohisa Ohmiya, Tomohiro Iwai, Martin C. Schwarzer, Seiji Mori, Tohru Taniguchi, Kenji Monde, Masaya Sawamura
  • Journal Title: Chem. Eur. J. Volume: 23 Issue: 35 Pages: 8400-8404
  • DOI: 10.1002/chem.201702070
  • Peer Reviewed / Open Access
• [Journal Article] Combined Theoretical and Experimental Studies of Nickel-Catalyzed Cross-Coupling of Methoxyarenes with Arylboronic Esters via C-O Bond Cleavage (2017)
  • Author(s): Martin C Schwarzer, Ryosuke Konno, Takayuki Hojo, Akimichi Ohtsuki, Keisuke Nakamura, Ayaka Yasutome, Hiroaki Takahashi, Toshiaki Shimasaki, Mamoru Tobisu, Naoto Chatani, Seiji Mori
  • Journal Title: J. Am. Chem. Soc. Volume: 139 Issue: 30 Pages: 10347-10358
  • DOI: 10.1021/jacs.7b04279
  • Peer Reviewed / Open Access
• [Journal Article] Characterization of Group 10-Metal-p-Substituted Phenoxyl Radical Complexes with Schiff Base Ligands. (2017)
  • Author(s): Oshita Hiromi、Kikuchi Misa、Mieda Kaoru、Ogura Takashi、Yoshimura Takayoshi、Tani Fumito、Yajima Tatsuo、Abe Hitoshi、Mori Seiji、Shimazaki Yuichi
  • Journal Title: ChemistrySelect Volume: 2 Issue: 31 Pages: 10221-10231
  • DOI: 10.1002/slct.201701986
  • Peer Reviewed / Open Access
• [Journal Article] Characterization of the one-electron oxidized Cu(II)-salen complexes with a side chain aromatic ring: the effect of the indole ring on the Cu(II)-phenoxyl radical species (2017)
  • Author(s): Oshita Hiromi、Yoshimura Takayoshi、Mori Seiji、Tani Fumito、Shimazaki Yuichi、Yamauchi Osamu
  • Journal Title: Journal of Biological Inorganic Chemistry Volume: 23 Issue: 1 Pages: 51-59
  • DOI: 10.1007/s00775-017-1508-6
  • Peer Reviewed / Open Access
• [Journal Article] Exploring Full Catalytic Cycle of Rhodium(I)-BINAP Catalyzed Isomerisation of Allylic Amines: A Graph Theoretical Approach for Path Optimisation (2017)
  • Author(s): Takayoshi Yoshimura, Satoshi Maeda, Tetsuya Taketsugu, Masaya Sawamura, Keiji Morokuma, Seiji Mori
  • Journal Title: Chemical Science Volume: 印刷中
  • Peer Reviewed / Open Access / Acknowledgement Compliant
• [Presentation] 不斉配位子複合型ニトロキシルラジカル/銅協奏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: 日本化学会 第98春季年会
• [Presentation] Experimental and comptutational investigations on the enantioselective alkynylation of α-ketosesters via copper catalysis (2017)
  • Author(s): Martin C Schwarzer, Takaoki Ishii , Hirohisa Ohmiya, Masaya Sawamura, Seiji Mori
  • Organizer: 日本化学会第97春季年会
  • Place of Presentation: 横浜
  • Year and Date: 2017-03-16
• [Presentation] Theoretical Studies of Molecular Activation Reactions -Mechanistic Insights and Rational Design of Catalysis- (2017)
  • Author(s): Seiji Mori
  • Organizer: Fifth Modeling of Chemical and Biological (Re)activity
  • Place of Presentation: Chennai, India
  • Year and Date: 2017-02-18
  • Int'l Joint Research / Invited
• [Presentation] Computational study of Ullmann coupling catalyzed by metal atoms (2017)
  • Author(s): Keita Urushibata, Ruiqin Zhang, and Seiji Mori
  • Organizer: 10th International Conference on Computational Physics
  • Place of Presentation: Macau, China
  • Year and Date: 2017-01-16
  • Int'l Joint Research
• [Presentation] Mechanistic Insights into Molecular Activation Reactions Based on Computational Chemistry (2017)
  • Author(s): Seiji Mori
  • Organizer: 10th International Conference on Computational Physics
  • Place of Presentation: Macau, China
  • Year and Date: 2017-01-16
  • Int'l Joint Research / Invited
• [Presentation] Computational Studies of Biosyntheses of Prostaglandins and Related Signaling Compounds (2017)
  • Author(s): Seiji Mori
  • Organizer: 6th Georgian Bay International Conference on Bioinorganic Chemistry
  • Int'l Joint Research / Invited
• [Presentation] Theoretical Study of Nickel-Catalyzed Cross-Coupling of Methoxyarenes with Arylboronic Esters via C-O Bond Cleavage (2017)
  • Author(s): Martin C Schwarzer, Ryosuke Konno, Takayuki Hojo, Akimichi Ohtsuki, Keisuke Nakamura, Ayaka Yasutome, Hiroaki Takahashi, Toshiaki Shimasaki, Mamoru Tobisu, Naoto Chatani, and Seiji Mori
  • Organizer: Big Data in Chemistry 53rd Symposium on Theoretical Chemistry
  • Int'l Joint Research
• [Presentation] Experimental and computational investigations on the enantioselective alkynylation of α-ketoesters via copper catalysis (2017)
  • Author(s): Martin Christoph Schwarzer, Takaoki Ishii, Akane Fujioka, Hirohisa Ohmiya, Masaya Sawamura, Seiji Mori
  • Organizer: 11th Triennial Congress of the World Association of Theoretical and Computational Chemists
  • Int'l Joint Research
• [Presentation] Graph theory approach in exploration of reaction path networks: Rh(I)BINAP-catalyzed isomerization of allylic amine (2017)
  • Author(s): Takayoshi Yoshimura, Satoshi Maeda, Tetsuya Taketsugu, Masaya Sawamura, Keiji Morokuma, Seiji Mori
  • Organizer: 11th Triennial Congress of the World Association of Theoretical and Computational Chemists
  • Int'l Joint Research
• [Presentation] Experimental and computational investigations on the enantioselective alkynylation of α-ketoesters via copper catalysis (2017)
  • Author(s): Martin Christoph Schwarzer, Takaoki Ishii, Akane Fujioka, Hirohisa Ohmiya, Masaya Sawamura, Seiji Mori
  • Organizer: 11th European Conference on Theoretical and Computational Chemistry
  • Int'l Joint Research
• [Presentation] Mechanistic Insights Into Transition-Metal Catalyzed Molecular Activation Reactions (2017)
  • Author(s): Seiji Mori
  • Organizer: eighth edition of Asia-Pacific Conference of Theoretical and Computational Chemistry
  • Int'l Joint Research / Invited
• [Presentation] Rh(I)-BINAP 触媒によるアリルアミンの異性化経路の探索とグラフを用いた経路最適化 (2017)
  • Author(s): 吉村 誠慶, 前田 理, 澤村 正也, 武次 徹也, 諸熊 奎治, 森 聖治
  • Organizer: 第20回理論化学討論会
• [Presentation] Theoretical Studies on Pd-Catalyzed Enantioselective Direct Allylation of 2-Alkylpyridines at the Side Chain α-Position (2017)
  • Author(s): Kyohei Kawashima,Ryo Murakami,Kentaro Sano,Tomohiro Iwai,Masaya Sawamura,Seiji Mori
  • Organizer: 錯体化学会第６７回討論会
• [Presentation] Theoretical Investigation of Enantioselective 1,4-Addition using Rhodium Catalysts with Planar-Chiral Phosphine-Olefin Ligands (2017)
  • Author(s): Takehiro Sato,Ken Kamikawa,Masamichi Ogasawara,Seiji Mori
  • Organizer: 錯体化学会第６７回討論会
• [Presentation] Theoretical Studies on Palladium-Catalyzed exo-Selective Cyanoesterification of Methyl Cyanoformate onto Norbornene (2016)
  • Author(s): Takuya Ishitsuka, Yasuhiro Okuda, Robert K. Szilagyi, Yasushi Nishihara, Seiji Mori
  • Organizer: International Symposium on C-O Bond Activation
  • Place of Presentation: Himeji, Hyogo
  • Year and Date: 2016-10-25
  • Int'l Joint Research / Invited
• [Presentation] Theoretical Study of Nickel-Catalyzed Cross-Coupling of Methoxyarenes with Arylboronic Esters via C-O Bond Cleavage (2016)
  • Author(s): Martin C. Schwarzer, Ryosuke Konno, H. Takahashi, Mamoru Tobisu, Naoto Chatani,Seiji Mori
  • Organizer: International Symposium on C-O Bond Activation
  • Place of Presentation: Himeji, Hyogo
  • Year and Date: 2016-10-25
  • Int'l Joint Research
• [Presentation] Experimental and Computational Investigations on the Enantioselective Alkynylation of α-Ketosesters via Copper Catalysis (2016)
  • Author(s): Martin C. Schwarzer, Takaoki Ishii, Hirohisa Ohmiya, Masaya Sawamura, Seiji Mori
  • Organizer: The 10th International Symposium on Homogeneous Catalysis (ISHCXX)
  • Place of Presentation: Kyoto
  • Year and Date: 2016-07-10
  • Int'l Joint Research
• [Presentation] Theoretical Study on Ni(0)-Catalyzed Cross-Coupling of Methoxyarenes with Arylboronic Esters via C-O Bond Activation (2016)
  • Author(s): Seiji Mori, Ryosuke Konno, Martin C. Schwarzer, H. Takahashi, Mamoru Tobisu, Naoto Chatani
  • Organizer: 10th congress on Electronic Structure: Principles and Applications
  • Place of Presentation: Castellon de la Plana, Spain
  • Year and Date: 2016-06-28
  • Int'l Joint Research
• [Presentation] Introduction of Quantum Beam Science and Applications to Chemistry and Related Sciences (2016)
  • Author(s): Seiji Mori
  • Organizer: 8th International Kasetsart University Science and Technology Annual Research Symposium
  • Place of Presentation: Bangkok, Thailand
  • Year and Date: 2016-06-02
  • Int'l Joint Research / Invited
• [Presentation] Computatinal study of Ullmann coupling catalyzed by a single metal atom (2016)
  • Author(s): 漆畑敬太、Rui-qin Zhang、森 聖治
  • Organizer: 第３２回化学反応討論会
  • Place of Presentation: さいたま
  • Year and Date: 2016-06-01
• [Presentation] Theoretical Insights into Molecular Activation Reactions (2016)
  • Author(s): Seiji Mori
  • Organizer: Thai-Japan Symposium in Chemistry
  • Place of Presentation: Chiang Mai, Thailand
  • Int'l Joint Research / Invited
• [Remarks] 理学部物理有機化学研究室
  • URL: http://smori.sci.ibaraki.ac.jp
• [Remarks] 森研究室ホームページ
  • URL: http://smori.sci.ibaraki.ac.jp/