金属中心キラリティーの精密制御に基づく配位アシンメトリーの新展開

• Project Area: Coordination Asymmetry: Design of Asymmetric Coordination Sphere and Anisotropic Assembly for the Creation of Functional Molecules
• Project/Area Number: 16H06509
• 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: The University of Tokyo
• Principal Investigator: 塩谷 光彦 東京大学, 大学院理学系研究科(理学部), 教授 (60187333)
• Co-Investigator(Kenkyū-buntansha): 馬越 啓介 長崎大学, 工学研究科, 教授 (20213481) ; 松下 信之 立教大学, 理学部, 教授 (80219427)
• Project Period (FY): 2016-06-30 – 2021-03-31
• Project Status: Granted (Fiscal Year 2020)
• Budget Amount: ¥169,390,000 (Direct Cost: ¥130,300,000、Indirect Cost: ¥39,090,000); Fiscal Year 2020: ¥21,190,000 (Direct Cost: ¥16,300,000、Indirect Cost: ¥4,890,000); Fiscal Year 2019: ¥22,100,000 (Direct Cost: ¥17,000,000、Indirect Cost: ¥5,100,000); Fiscal Year 2018: ¥21,190,000 (Direct Cost: ¥16,300,000、Indirect Cost: ¥4,890,000); Fiscal Year 2017: ¥19,500,000 (Direct Cost: ¥15,000,000、Indirect Cost: ¥4,500,000); Fiscal Year 2016: ¥85,410,000 (Direct Cost: ¥65,700,000、Indirect Cost: ¥19,710,000)
• Keywords: 配位アシンメトリー / キラル金属錯体 / 不斉合成 / 異方集積化 / 錯体化学 / 金属錯体 / 非対称配位圏 / 不斉吸着 / 不斉誘導 / プロキラル分子

Outline of Annual Research Achievements

本研究は、金属元素を立体制御、反応場、物性発現の場と捉え、これまで未開拓であった金属錯体における非対称配位圏の設計・合成と異方集積化法を理論・実験・計測により開拓することを目的とした。
2019年度は、先に開発した四面体型の亜鉛錯体およびオキソバナジウム(V=O)に加えて、四面体型の鉄錯体の合成に焦点を当てた。ニトロシル基を有する鉄(0)トリカルボニル錯体を出発原料とし、カルベン型配位子とジアゾ配位子をァルボニル配位子と交換し、ラセミ体のChiral-at-iron錯体の合成に成功した。鉄ニトロシル錯体の鉄の酸化数は永年議論されていたが、本研究でメスバウアー測定などを駆使し、鉄(II)に酸化されていることが明らかになった。次の課題である光学分割を現在検討中である。また、キラルな亜鉛錯体による不斉反応の反応条件の最適化を進め、最高91% eeに不斉収率を得ることができた。さらに、キラルなオキソバナジウム錯体の不斉誘導を進め、光学純度の向上のための反応条件を検討中である。
これら以外に、キラルなカルベン型配位子を用いた炭素中心の金(I)クラスターの合成に成功し、金6核部分の歪みにより炭素中心キラリティーの発生に成功した。この歪みは、溶液中でも維持されることがわかり、その安定性と配位子の構造との相関関係も明らかになった。今年度の研究実績の一部は、国際学術誌3報に発表され、国内外で高く評価されている。

Current Status of Research Progress

2: Research has progressed on the whole more than it was originally planned.

Reason

以下に、今年度の代表的な研究成果と共同研究体制を示し、本研究がおおむね順調に進展している理由を述べる。
1. 金属中心キラリティーを有する亜鉛錯体の不斉誘導および不斉反応への応用：アキラルな非対称三座配位子を用いて、キラルな四面体型金属錯体を構築した。ラセミ体平衡混合物に光学活性な単座配位子(アミノアルコール)を不斉補助剤を配位させることにより、ジアステレオマー比が50:1まで大きく偏ることがわかった（96％ de）。この亜鉛錯体に配位した不斉補助剤をアキラルなニトリル配位子に置換し結晶化したところ、99.9%以上の光学純度をもつchiral-at-zinc錯体を得ることができ、非プロトン性溶媒中では亜鉛中心の絶対配置と光学純度が保たれることが明らかになった。本錯体を不斉オキサ・ディールス・アルダー反応の触媒として用い、室温で87% eeの不斉収率を達成できた。
2. オキソバナジウム錯体の金属中心キラリティーの動的平衡制御：フェノール性アルコラートを配位ドナーとする非対称二座配位子を用いて、キラルなオキソバナジウム錯体を合成した。光学活性配位子を用いて、ジアステレオ選択的な反応を検討中である。
3. ニトロシル基を有する鉄(0)トリカルボニル錯体を出発原料とし、カルベン型配位子とジアゾ配位子をァルボニル配位子と交換し、ラセミ体のChiral-at-iron錯体の合成に成功した。鉄ニトロシル錯体の鉄の酸化数は永年議論されていたが、本研究でメスバウアー測定などを駆使し、鉄(II)に酸化されていることが明らかになった。次の課題である光学分割を現在検討中である。
【領域内共同研究】江原G (A01)と理論分子設計、分子間相互作用および反応機構に関する理論研究を行った。
【国際共同研究】コロナ禍のため、オンラインによりドイツのMeggers G等と情報共有を行った。

Strategy for Future Research Activity

2020年度は3名の研究協力者、1名のポスドク、5名の大学院生を配置し、以下の研究実施計画を遂行する予定である。
1. 金属中心キラリティーを有する窒化モリブデン錯体の合成と動的平衡制御：アキラルな非対称二座配位子は、四面体型窒化金属(M=N-)錯体に金属中心キラリティーを生じさせることが可能である。多くの窒化金属錯体は触媒能を有するため、不斉反応への発展が期待される。亜鉛およびオキソバナジウム錯体の結果を踏まえて、ラセミ混合物の動的平衡制御を試み、金属中心の絶対配置と配置安定性を調べる。また、それらを用いて様々な不斉触媒反応を検討する。
2. 亜鉛錯体に用いた非対称三座配位子を用いて、四面体型ニッケルおよびコバルト錯体を合成し、酸化還元触媒への適用を検討する。
3. カルベン型配位子を用いた炭素中心の金(I)クラスターの合成法を基に、銀(I)イオンやCu(I)イオンを含む構造的に非対称なヘテロ金属クラスターへの展開を図る。また、キラルなカルベン型配位子の結合に誘起される金6核部分の歪みにより炭素中心キラリティーを発生させ、これらの溶液中および結晶中の物性や反応性を調べる。

Research Products

• [Int'l Joint Research] University of Marburg/University of Bonn/University of Muenster(ドイツ)
• [Int'l Joint Research] Tsinghua University/East China Normal University(中国)
• [Int'l Joint Research] University of Birmingham(英国)
• [Int'l Joint Research] University of Marburg/Technical University of Dortmund/University of Muenster(ドイツ)
• [Int'l Joint Research] University of Amsterdam(オランダ)
• [Int'l Joint Research] East China Normal University(中国)
• [Int'l Joint Research] University of Birmingham(英国)
• [Int'l Joint Research] University of Marburg/Technical University of Dortmund/University of Muenster(Germany)
• [Int'l Joint Research] The University of Edinburgh/University of Birmingham(United Kingdom)
• [Int'l Joint Research] University of Amsterdam(オランダ)
• [Int'l Joint Research] East China Normal University(China)
• [Int'l Joint Research] Indiana University(米国)
• [Int'l Joint Research]
• [Journal Article] Multi-Stimuli Responsive Interconversion between Bowl- and Capsule-Shaped Self-Assembled Zinc(II) Complexes (2020)
  • Author(s): K. Endo, H. Ube, M. Shionoya
  • Journal Title: Journal of the American Chemical Society Volume: 142 Pages: 407-416
  • DOI: 10.1021/jacs.9b11099
  • Peer Reviewed
• [Journal Article] Supramolecular DNA Three-way Junction Motifs with a Bridging Metal Center (2020)
  • Author(s): Y. Takezawa, M. Shionoya
  • Journal Title: Frontiers in Chemistry Volume: 7 Pages: 925-925
  • DOI: 10.3389/fchem.2019.00925
  • Peer Reviewed / Open Access
• [Journal Article] Self-assembled Porphyrin-based Cage Complexes, M₁₁L₆ (M = Zn^II, Cd^II), with Inner Coordination Sites in Their Crystal Structure (2020)
  • Author(s): F. Iizuka, H. Ube, H. Sato, T. Nakamura, M. Shionoya
  • Journal Title: Chem. Lett. Volume: 49 Issue: 3 Pages: 323-326
  • DOI: 10.1246/cl.190943
  • NAID: 130007805920
  • ISSN: 0366-7022, 1348-0715
  • Peer Reviewed
• [Journal Article] Novel Porous Crystals with Macrocycle-Based Well-Defined Molecular Recognition Sites (2020)
  • Author(s): S. Tashiro, and M. Shionoya
  • Journal Title: Accounts of Chemical Research Volume: 53 Pages: 632-643
  • DOI: 10.1021/acs.accounts.9b00566
  • Peer Reviewed
• [Journal Article] Core-Shell Metal-Macrocycle Framework (MMF): Spatially Selective Dye Inclusion through Core-to-Shell Anisotropic Transport along Crystalline 1D-Channels Connected by Epitaxial Growth (2020)
  • Author(s): S. Tashiro, S. Mitsui, D. W. Burke, R. Kubota, N. Matsushita, M. Shionoya
  • Journal Title: CrystEngComm Volume: 22 Pages: 1306-1309
  • DOI: 10.1039/d0ce00120a
  • Peer Reviewed
• [Journal Article] Ligand Effects on the Photophysical Properties of N,N’-Diisopropylbenzimidazolydene-Protected C-Centered Hexagold(I) Clusters (2020)
  • Author(s): Z. Lei, K. Nagata, H. Ube, M. Shionoya
  • Journal Title: Journal of Organometallic Chemistry Volume: 917 Pages: 121271-121271
  • Peer Reviewed
• [Journal Article] Synthesis of Hetero-multinuclear Metal Complexes by Site-Selective Redox Switching and Transmetalation on a Homo-multinuclear Complex (2019)
  • Author(s): H. Ube, K. Endo, H. Sato, M. Shionoya
  • Journal Title: Journal of the American Chemical Society Volume: 141 Pages: 10384-10389
  • DOI: 10.1021/jacs.9b04123
  • Peer Reviewed
• [Journal Article] Molecular Recognition of Planar and Non-Planar Aromatic Hydrocarbons through Multipoint Ag-π Bonding in a Dinuclear Metallo-Macrocycle (2019)
  • Author(s): K. Omoto, S. Tashiro, M. Shionoya
  • Journal Title: Chemical Science Volume: 10 Pages: 7172-7176
  • DOI: 10.1039/c9sc02619c
  • Peer Reviewed
• [Journal Article] Enzymatic Synthesis of Cu(II)-responsive Deoxyribozymes through Polymerase Incorporation of Artificial Ligand-type Nucleotides (2019)
  • Author(s): Y. Takezawa, T. Nakama, M. Shionoya
  • Journal Title: Journal of the American Chemical Society Volume: 141 Pages: 19342-19350
  • DOI: 10.1021/jacs.9b08955
  • Peer Reviewed
• [Journal Article] A Carbon-Centered Hexagold(I) Cluster Supported by N-Heterocyclic Carbene Ligands (2018)
  • Author(s): H. Ube, Q. Zhang, M. Shionoya
  • Journal Title: Organometallics Volume: 37 Pages: 2007-2009
  • DOI: 10.1021/acs.organomet.8b00291
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Rational synthesis of benzimidazole[3]arenes by CuII-catalyzed post-macrocyclization transformation (2018)
  • Author(s): Tashiro Shohei、Umeki Tsutomu、Kubota Ryou、Shionoya Mitsuhiko
  • Journal Title: Chem. Sci. Volume: 9 Pages: 7614-7619
  • DOI: 10.1039/c8sc03086c
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Preferential Photoreaction in a Porous Crystal, Metal-Macrocycle Framework: PdII-Mediated Olefin Migration over [2+2] Cycloaddition (2018)
  • Author(s): H. Yonezawa, S. Tashiro, T. Shiraogawa, M. Ehara, R. Shimada, T. Ozawa, M. Shionoya
  • Journal Title: J. Am. Chem. Soc. Volume: 140 Pages: 16610-16614
  • DOI: 10.1021/jacs.8b08534
  • Peer Reviewed
• [Journal Article] Metal-centred azaphosphatriptycene gear with a photo- and thermally driven mechanical switching function based on coordination isomerism (2017)
  • Author(s): Hitoshi Ube, Yoshihiro Yasuda, Hiroyasu Sato, Mitsuhiko Shionoya
  • Journal Title: Nature Communications Volume: 8 Pages: 14296-14296
  • DOI: 10.1038/ncomms14296
  • Peer Reviewed / Open Access / Acknowledgement Compliant
• [Journal Article] Artificial DNA Base Pairing Mediated by Diverse Metal Ions (2017)
  • Author(s): Makoto Ebine, Yuri Takada, Naoto Yanai, and Tohru Oishi
  • Journal Title: Chem. Lett. Volume: 46 Issue: 5 Pages: 622-633
  • DOI: 10.1246/cl.160985
  • NAID: 130005655669
  • ISSN: 0366-7022, 1348-0715
  • Peer Reviewed / Open Access / Int'l Joint Research / Acknowledgement Compliant
• [Journal Article] Arrangement of Proteinogenic α-Amino Acids on a Cyclic Peptide comprising Alternate Biphenyl-Cored ζ-Amino Acids (2017)
  • Author(s): S. Tashiro, M. Chiba, M. Shionoya
  • Journal Title: Chem. Asian J. Volume: 12 Pages: 1087-1094
  • DOI: 10.1002/asia.201700203
  • Peer Reviewed
• [Journal Article] Chiral Metallosupramolecular Architectures (2017)
  • Author(s): L.-J. Chen, H.-B. Yang, M. Shionoya
  • Journal Title: Chemical Society Reviews Volume: 46 Pages: 2555-2576
  • DOI: 10.1039/c7cs00173h
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Multifunctional Octamethyltetrasila[2.2]cyclophanes: Conformational Variations, Circularly Polarized Luminescence, and Organic Electroluminescence (2017)
  • Author(s): Shimada Masaki、Yamanoi Yoshinori、Ohto Tatsuhiko、Pham Song-Toan、Yamada Ryo、Tada Hirokazu、Omoto Kenichiro、Tashiro Shohei、Shionoya Mitsuhiko、Hattori Mineyuki、Jimura Keiko、Hayashi Shigenobu、Koike Hikaru、Iwamura Munetaka、Nozaki Koichi、Nishihara Hiroshi
  • Journal Title: Journal of the American Chemical Society Volume: 139 Pages: 11214-11221
  • DOI: 10.1021/jacs.7b05671
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] A Circularly Arranged Sextupled Triptycene Gear Molecule (2017)
  • Author(s): H. Ube, R. Yamada, J. Ishida, H. Sato, M. Shiro, M. Shionoya
  • Journal Title: Journal of the American Chemical Society Volume: 139 Pages: 16470-16473
  • DOI: 10.1021/jacs.7b09439
  • Peer Reviewed
• [Journal Article] Chiral Metallosupramolecular Architectures (2017)
  • Author(s): Li-Jun Chen, Hai-Bo Yang, Mitsuhiko Shionoya
  • Journal Title: Chem. Soc. Rev. Volume: 印刷中
  • Peer Reviewed / Int'l Joint Research / Acknowledgement Compliant
• [Journal Article] pH-Dependence of the Thermal Stability of Metallo-DNA Duplexes Containing Ligand-Type 5-Hydroxyuracil Nucleobases (2016)
  • Author(s): Kotaro Nishiyama, Yusuke Takezawa, Mitsuhiko Shionoya
  • Journal Title: Inorganic Chimica Acta Volume: 452 Pages: 176-180
  • DOI: 10.1016/j.ica.2016.04.040
  • Peer Reviewed / Acknowledgement Compliant
• [Presentation] Supramolecular Coordination Chemistry: Array, Space, and Motion (2019)
  • Author(s): Mitsuhiko Shionoya
  • Organizer: 表年 1st Meeting of Core-to-Core Program on Coordination Nanosheet
  • Int'l Joint Research / Invited
• [Presentation] Complexity in Coordination-Driven Self-Assembly: Molecular Design and Serendipity (2019)
  • Author(s): Mitsuhiko Shionoya
  • Organizer: The 30th Anniversary Todai-Unisra Symposium on “Complexity”（
  • Int'l Joint Research / Invited
• [Presentation] Metal-responsive DNAzymes based on Metal-mediated DNA Base Pairing (2019)
  • Author(s): Mitsuhiko Shionoya
  • Organizer: ICBIC2019 -19th International Conference on Biological Inorganic Chemistry
  • Int'l Joint Research / Invited
• [Presentation] Molecular Design and Serendipity in Coordination-Driven Self-Assembly (2019)
  • Author(s): Mitsuhiko Shionoya
  • Organizer: QSCC2019
  • Int'l Joint Research / Invited
• [Presentation] Coordination Asymmetry In Supramolecular Chemistry (2019)
  • Author(s): Mitsuhiko Shionoya
  • Organizer: Complex Systems Made Simple
  • Int'l Joint Research / Invited
• [Presentation] Coordination-Driven Self-Assembly: Design and Serendipity (2019)
  • Author(s): Mitsuhiko Shionoya
  • Organizer: 12th China-Japan Joint Symposium on Metal Cluster Compounds
  • Int'l Joint Research / Invited
• [Presentation] Coordination Asymmetry in Supramolecular Architectures (2019)
  • Author(s): Mitsuhiko Shionoya
  • Organizer: EPSRC-JSPS Core-to-Core International Workshop on Two-Dimensional Coordination Nanosheets
  • Int'l Joint Research / Invited
• [Presentation] Coordination Asymmetry based on Supramolecular Porous Crystals (2018)
  • Author(s): M. Shionoya
  • Organizer: International Symposium on Macrocyclic and Supramolecular Chemistry
  • Int'l Joint Research / Invited
• [Presentation] 超分子金属錯体：配列、空間、モーション (2018)
  • Author(s): 塩谷光彦
  • Organizer: 錯体化学会第68回討論会
  • Invited
• [Presentation] Molecular Behavior in Supramolecular Spaces (2018)
  • Author(s): M. Shionoya
  • Organizer: International Conference on Coordination Chemistry 2018
  • Int'l Joint Research / Invited
• [Presentation] Metal-mediated Supramolecular Array, Space and Motion (2018)
  • Author(s): M. Shionoya
  • Organizer: iJaDe2018: From Molecules to Materials
  • Int'l Joint Research / Invited
• [Presentation] Rational Design of Metal-based Supermolecules (2018)
  • Author(s): M. Shionoya
  • Organizer: 第28回光学活性化合物シンポジウム
  • Invited
• [Presentation] 超分子金属錯体の精密設計：配列、空間、モーション (2018)
  • Author(s): 塩谷光彦
  • Organizer: 近畿化学協会 有機金属部会平成３０年度第３回例会
  • Invited
• [Presentation] Metal-based Supramolecular Array, Space and Motion (2018)
  • Author(s): M. Shionoya
  • Organizer: MANA International Symposium 2018 Towards Perceptive Nanomaterials, Devices and Systems
  • Int'l Joint Research / Invited
• [Presentation] Design and Observation of Supramolecular Behaviors with Switching Functions (2017)
  • Author(s): M. Shionoya
  • Organizer: Gordon Research Conference: Artificial Molecular Switches & Motors
  • Int'l Joint Research / Invited
• [Presentation] Metal-based Supramolecular Array, Space and Motion (2017)
  • Author(s): M. Shionoya
  • Organizer: ResMoSys 2017
  • Int'l Joint Research / Invited
• [Presentation] NANOSPACE-SPECIFIC MOLECULAR BEHAVIORS (2017)
  • Author(s): 6th Asian Conference on Coordination Chemistry
  • Organizer: M. Shionoya
  • Int'l Joint Research / Invited
• [Presentation] Dynamic Molecular Behaviors in Confined Supramolecular Spaces (2017)
  • Author(s): M. Shionoya
  • Organizer: JPN-US bilateral meeting
  • Int'l Joint Research / Invited
• [Presentation] Unexpected Molecular Behaviors in Supramolecular Porous Crystals (2017)
  • Author(s): M. Shionoya
  • Organizer: 11th Japan-China Joint Symposium on Metal Cluster Compounds
  • Int'l Joint Research / Invited
• [Presentation] Supramolecular Asymmetry Induction (2017)
  • Author(s): M. Shionoya
  • Organizer: The 3rd International Symposium on Center of Excellence for Innovative Material Sciences Based on Supramolecules
  • Int'l Joint Research / Invited
• [Presentation] 非対称超分子空間の構築と機能化 (2017)
  • Author(s): 塩谷光彦
  • Organizer: 日本化学会第97春季年会
  • Place of Presentation: 慶応義塾大学（神奈川県横浜市）
  • Invited
• [Presentation] Metal-based Supramolecular Array, Space and Motion (2016)
  • Author(s): Mitsuhiko Shionoya
  • Organizer: RSC Macrocyclic and Supramolecular Meeting (MASC-2016)
  • Place of Presentation: Edinburgh (UK)
  • Year and Date: 2016-12-15
  • Int'l Joint Research / Invited
• [Presentation] Supramolecular Design for Metal Array, Space, and Motion (2016)
  • Author(s): Mitsuhiko Shionoya
  • Organizer: Chile-Japan Academic Forum 2016: Satellite Meeting at Santiago
  • Place of Presentation: Santiago (Chile)
  • Int'l Joint Research / Invited
• [Book] Self-Assemblies Based on Metal-Mediated Artificial Nucleobase Pairing (2017)
  • Author(s): Yusuke Takezawa, Jens Muller, Mitsuhiko Shionoya
  • Publisher: Elsevier
• [Remarks] 塩谷研究室 Bioinorganic Chemistry Laboratory
  • URL: http://www.chem.s.u-tokyo.ac.jp/users/bioinorg/index.html
• [Remarks] 配位アシンメトリー：非対称配位圏設計と異方集積化が拓く新物質科学
  • URL: http://www.asymmetallic.jp
• [Remarks] 塩谷研究室 Bioinorganic Chemistry Laboratory
  • URL: http://www.chem.s.u-tokyo.ac.jp/users/bioinorg/Index.html
• [Funded Workshop] QSCC2019 (2019)
• [Funded Workshop] 12th China-Japan Joint Symposium on Metal Cluster Compounds (2019)