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量子化学計算に基づく分子活性化の活性種および反応機構の解明

Publicly Offered Research

Project AreaMolecule Activation Directed toward Straightforward Synthesis
Project/Area Number 25105707
Research Category

Grant-in-Aid for Scientific Research on Innovative Areas (Research in a proposed research area)

Allocation TypeSingle-year Grants
Review Section Science and Engineering
Research InstitutionIbaraki University

Principal Investigator

森 聖治  茨城大学, 理学部, 教授 (50332549)

Project Period (FY) 2013-04-01 – 2015-03-31
Project Status Completed (Fiscal Year 2014)
Budget Amount *help
¥7,020,000 (Direct Cost: ¥5,400,000、Indirect Cost: ¥1,620,000)
Fiscal Year 2014: ¥3,510,000 (Direct Cost: ¥2,700,000、Indirect Cost: ¥810,000)
Fiscal Year 2013: ¥3,510,000 (Direct Cost: ¥2,700,000、Indirect Cost: ¥810,000)
Keywords結合開裂 / 金属触媒 / 密度汎関数法計算 / 分子活性化 / 量子化学計算 / 反応機構 / 反応活性種
Outline of Annual Research Achievements

今年度は、Pd触媒のC-C結合活性化で始まるノルボルナジエンのシアノエステル化反応機構の理論的解明、エポキシドと二酸化炭素の共重合の効率的鉄(III)触媒の設計に関する計算科学的研究などを行った。
(1) 本研究ではノルボルネン、Pd(PPh3)4 およびシアノギ酸メチルから生成する活性種trans-[PdII(CN)(COOMe)(PPh3)2] を計算モデルとして検討を行った。その結果、活性種からPPh3 1分子が脱離し、オレフィンがパラジウムに配位する段階において endo のπ錯体に比べ、exo のπ錯体がエネルギー的に安定であり、各反応段階においても exoで反応する経路がエネルギー的に安定であることが分かった。この結果は実験の選択性を説明できる。さらに、exoのπ錯体の方が、ノルボルネンのπ軌道とPdの孤立空軌道の重なりが大きいことが、exo選択性を説明できることが判明した。
(2)プロピレンオキシドと二酸化炭素の共重合反応において、高いPPC選択性を持つ、かさ高い置換基を有するFe(III)-コロール錯体を、密度汎関数法計算により錯体とエポキシドおよび生成物のアルコキシドが金属に配位するエネルギーの差を計算することにより、設計した。
(3)植物ホルモン様物質の生合成過程で重要な、シトクロムP450による脂肪族ペルオキシドからアレンオキシドの生合成反応機構を、QM/MM法によって検討した。アレンオキシドのO-O結合の解離により、Fe-OH結合の生成、エポキシドの生成などの反応経路を解明した。さらに、プロトン共役電子移動(PCET)は、水分子が加わると遅くなることを示した。以上の研究成果は論文に掲載された。

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。

Report

(2 results)
  • 2014 Annual Research Report
  • 2013 Annual Research Report
  • Research Products

    (26 results)

All 2015 2014 2013 Other

All Journal Article (8 results) (of which Peer Reviewed: 8 results,  Open Access: 1 results,  Acknowledgement Compliant: 5 results) Presentation (16 results) (of which Invited: 6 results) Remarks (2 results)

  • [Journal Article] Theoretical Studies of Rhodium-Catalyzed Borylation of Nitriles through Cleavage of Carbon-Cyano Bonds2014

    • Author(s)
      Hirotaka Kinuta, Hiroaki Takahashi, Mamoru Tobisu, Seiji Mori, and Naoto Chatani
    • Journal Title

      Bull Chem Soc Jpn

      Volume: 87 Issue: 6 Pages: 655-669

    • DOI

      10.1246/bcsj.20130332

    • NAID

      130004059118

    • Related Report
      2014 Annual Research Report 2013 Annual Research Report
    • Peer Reviewed / Open Access / Acknowledgement Compliant
  • [Journal Article] The Origin of Exo-Selectivity in Methyl Cyanoformate Addition onto the C=C Bond of Norbornene in Pd-Catalyzed Cyanoesterification2014

    • Author(s)
      Y. Okuda, R. Szilagyi, S. Mori, and Y. Nishihara
    • Journal Title

      Dalton Transaction

      Volume: 43 Issue: 25 Pages: 9537-9548

    • DOI

      10.1039/c4dt00839a

    • Related Report
      2014 Annual Research Report 2013 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Redox Chemistry of Nickel(II)-Complexes Supported by a Series of Non-innocent β-Diketiminate Ligands2014

    • Author(s)
      June Takaichi, Yuma Morimoto, Kei Ohkubo, Chizu Shimokawa, Takayuki Hojo, Seiji Mori, Haruyasu Asahara, Hideki Sugimoto, Nobutaka Fujieda, Nagatoshi Nishiwaki, Shunichi Fukuzumi, and Shinobu Itoh
    • Journal Title

      Inorganic Chemistry

      Volume: 53 Issue: 12 Pages: 6159-6169

    • DOI

      10.1021/ic5006693

    • Related Report
      2014 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Mechanistic Insights into the Catalytic Reaction of Plant Allene Oxide Synthase (pAOS) via QM and QM/MM Calculations2014

    • Author(s)
      Tuanjai Somboon, Jun Ochiai, Witcha Treesuwan, M. Paul Gleeson, Supa Hannongbua,Seiji Mori
    • Journal Title

      J. Mol. Graph. Model.

      Volume: 52 Pages: 20-29

    • DOI

      10.1016/j.jmgm.2014.05.012

    • Related Report
      2014 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Facile Estimation of Catalytic Activity and Selectivities in Copolymerization of Propylene Oxide with Carbon Dioxide Mediated by Metal Complexes with Planer Tetradentate Ligand2014

    • Author(s)
      Takahiro Ohkawara, Kohei Suzuki, Koji Nakano, Seiji Mori, and Kyoko Nozaki
    • Journal Title

      J. Am. Chem. Soc.

      Volume: 136 Issue: 30 Pages: 10728-10735

    • DOI

      10.1021/ja5046814

    • Related Report
      2014 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Experimental and Theoretical Studies on the Platinum-Mediated Selective C(sp)-Si Bond Cleavage of Alkynylsilanes2014

    • Author(s)
      Yasuhiro Okuda, Yuya Ishiguro, Seiji Mori, Kiyohiko Nakajima, Yasushi Nishihara
    • Journal Title

      Organometallics

      Volume: 33 Issue: 7 Pages: 1878-1889

    • DOI

      10.1021/om5002588

    • Related Report
      2013 Annual Research Report
    • Peer Reviewed
  • [Journal Article] An efficient access to aspermytin A and oblongolide C through an intramolecular nitrile oxide-alkene [3+2] cycloaddition2013

    • Author(s)
      Inoue A
    • Journal Title

      Synlett

      Volume: 24 Issue: 01 Pages: 61-64

    • DOI

      10.1055/s-0032-1317693

    • Related Report
      2013 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Cooperative Catalysis of Metal and O-H-O/sp3-C-H-O Two-point Hydrogen Bonds in Alcoholic Solvents: Copper-catalyzed Enantioselective Direct Alkynylation of Aldehydes with Terminal Alkynes2013

    • Author(s)
      Takaoki Ishii, Ryo Watanabe, Toshimitsu Moriya, Hirohisa Ohmiya, Seiji Mori, Masaya Sawamura
    • Journal Title

      Chem. Eur. J.

      Volume: 19 Issue: 40 Pages: 13547-13553

    • DOI

      10.1002/chem.201301280

    • Related Report
      2013 Annual Research Report
    • Peer Reviewed
  • [Presentation] 鉄(III)ポルフィリン―チオレート錯体の構造と電子状態に関する研究2015

    • Author(s)
      吉村 誠慶・内田 ひかる・落合 純・鈴木 潤・近藤 圭佑・樋口 恒彦・森 聖治
    • Organizer
      日本化学会第95春季年会
    • Place of Presentation
      船橋
    • Year and Date
      2015-03-26 – 2015-03-29
    • Related Report
      2014 Annual Research Report
  • [Presentation] Computational studies on complex mechanisms of organic and biological reactions2015

    • Author(s)
      Seiji Mori
    • Organizer
      International workshop on "Theoretical Chemistry on Functional Biomolecular Systems"
    • Place of Presentation
      札幌
    • Year and Date
      2015-02-10
    • Related Report
      2014 Annual Research Report
    • Invited
  • [Presentation] Theoretical Studies of Molecular Activation Reactions -Mechanistic Insights and Rational Design of Catalysis-2014

    • Author(s)
      Seiji Mori
    • Organizer
      The Second International Workshop on Computational Science and Engineering
    • Place of Presentation
      Hong Kong
    • Year and Date
      2014-12-13 – 2014-12-16
    • Related Report
      2014 Annual Research Report
    • Invited
  • [Presentation] Theoretical Studies on Palladium-Catalyzed exo-Selective Cyanoesterification of Methyl Cyanoformate onto Norbornene2014

    • Author(s)
      Takuya Ishitsuka, Yasuhiro Okuda, Robert K. Szilagyi, Yasushi Nishihara, Seiji Mori
    • Organizer
      The Second International Workshop on Computational Science and Engineering
    • Place of Presentation
      Hong Kong
    • Year and Date
      2014-12-13 – 2014-12-16
    • Related Report
      2014 Annual Research Report
  • [Presentation] Computational Studies on Metal-mediated C-C and C-H Bond Cleavage Reactions in Organometallic/Bioinorganic Chemistry2014

    • Author(s)
      Seiji Mori
    • Organizer
      14 QSCP
    • Place of Presentation
      Tamsui, Taiwan
    • Year and Date
      2014-11-11 – 2014-11-17
    • Related Report
      2014 Annual Research Report
  • [Presentation] Computational Studies of Mechanistic Insight into Synthases of Prostaglandins and Related Signaling Compounds2014

    • Author(s)
      Seiji Mori
    • Organizer
      Vietnam Malaysian International Chemical Congress
    • Place of Presentation
      Hanoi, Vietnam
    • Year and Date
      2014-11-07 – 2014-11-09
    • Related Report
      2014 Annual Research Report
    • Invited
  • [Presentation] Exploring Full Catalytic Cycle of Rh(I)-BINAP Catalyzed Isomerization of Allylamines2014

    • Author(s)
      Takayoshi Yoshimura, Satoshi Maeda, Masaya Sawamura, Tetsuya Taketsugu, Keiji Morokuma, Seiji Mori
    • Organizer
      The 2nd international conference on organometallics and catalysis
    • Place of Presentation
      Nara
    • Year and Date
      2014-10-26 – 2014-10-29
    • Related Report
      2014 Annual Research Report
  • [Presentation] パラジウム触媒を用いたノルボルネンのシアノエステル化反応におけるexo選択性の理論的解明2014

    • Author(s)
      石塚 拓也, 奥田 靖浩, Robert K Szilagyi, 西原 康師, 森 聖治
    • Organizer
      日本コンピュータ化学会2014秋季年会
    • Place of Presentation
      郡山
    • Year and Date
      2014-10-18 – 2014-10-19
    • Related Report
      2014 Annual Research Report
  • [Presentation] Rh(I)-BINAP触媒によるアリルアミンの1,3-不斉水素転移反応に関する理論的研究2014

    • 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
      日本コンピュータ化学会2014秋季年会
    • Place of Presentation
      郡山
    • Year and Date
      2014-10-18 – 2014-10-19
    • Related Report
      2014 Annual Research Report
  • [Presentation] Theoretical Studies on Biosynthesis of Prostaglandin G2 by Cyclooxygenase-22014

    • Author(s)
      Seiji Mori
    • Organizer
      ANSCSE 18
    • Place of Presentation
      Pattaya, Thailand
    • Related Report
      2013 Annual Research Report
    • Invited
  • [Presentation] 反応機構解析に基づく二酸化炭素とエポキシドの交互共重合触媒の開発2014

    • Author(s)
      大河原 昂広, 中野 幸司, 森 聖治、野崎京子
    • Organizer
      日本化学会第94春季年会
    • Place of Presentation
      名古屋
    • Related Report
      2013 Annual Research Report
  • [Presentation] Quantum Chemical and Experimental Studies on Copper-catalyzed Enantioselective Direct Alkynylation of Aldehydes with Terminal Alkynes2013

    • Author(s)
      Seiji Mori, R. Watanabe, T. Ishii ,T. Moriya, H. Ohmiya, M. Sawamura
    • Organizer
      APCTCC-6
    • Place of Presentation
      Gyeongju, South Korea
    • Related Report
      2013 Annual Research Report
    • Invited
  • [Presentation] Computational studies on C-C and C-H bond activation reactions in organic and biological chemistry2013

    • Author(s)
      Seiji Mori
    • Organizer
      2013 WFTCPC
    • Place of Presentation
      Chon Buri, Thailand
    • Related Report
      2013 Annual Research Report
    • Invited
  • [Presentation] Ni(II)ビス(β-ジケチミネート)錯体の構造および電子状態に関するDFT計算2013

    • Author(s)
      北條 貴之・高市 準・森 聖治・杉本 秀樹・藤枝 伸宇・伊東 忍
    • Organizer
      錯体化学会第63回討論会
    • Place of Presentation
      那覇
    • Related Report
      2013 Annual Research Report
  • [Presentation] Rh(I)-BINAP触媒によるアリルアミンの1,3-不斉水素転位反応に関する理論的研究2013

    • Author(s)
      吉村 誠慶・前田 理・澤村 正也・諸熊 奎治・森 聖治
    • Organizer
      錯体化学会第63回討論会
    • Place of Presentation
      那覇
    • Related Report
      2013 Annual Research Report
  • [Presentation] シクロオキシゲナーゼ-2によるプロスタグランジンG2の生合成経路に関する酵素の効果の研究2013

    • Author(s)
      吉村 誠慶,Gleeson Paul,Hannongbua Supa,森 聖治
    • Organizer
      分子科学討論会2013
    • Place of Presentation
      京都
    • Related Report
      2013 Annual Research Report
  • [Remarks] 森研究室ホームぺージ

    • URL

      http://smori.sci.ibaraki.ac.jp

    • Related Report
      2014 Annual Research Report
  • [Remarks] 森研究室ホームページ

    • URL

      http://smori.sci.ibaraki.ac.jp

    • Related Report
      2013 Annual Research Report

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Published: 2013-05-15   Modified: 2019-07-29  

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