面不斉アミノメタロセニルカルベン金属錯体触媒の開発

• Project Area: Precise Formation of a Catalyst Having a Specified Field for Use in Extremely Difficult Substrate Conversion Reactions
• Project/Area Number: 18H04236
• Research Category: Grant-in-Aid for Scientific Research on Innovative Areas (Research in a proposed research area)
• Allocation Type: Single-year Grants
• Research Institution: Chiba University
• Principal Investigator: 吉田 和弘 千葉大学, 大学院理学研究院, 准教授 (60375607)
• 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: NHC / 金属錯体触媒 / メタロセン / 面不斉

Outline of Annual Research Achievements

不斉NHC配位子の開発は、遷移金属錯体触媒を利用する有機合成分野における重要な課題の一つである。我々はここ数年、フェロセンを母核に持つ新たな面不斉NHC（N-ヘテロサイクリックカルベン）配位子、環状アミノフェロセニルカルベン（Cyclic (Amino)(ferrocenyl)carbene: CAFeC）の開発を行ってきた。これまでに七員環CAFeCや六員環CAFeCを報告しており、特に、七員環CAFeCに関しては、不斉ホウ素共役付加反応や不斉水素移動反応において、良好な不斉配位子として利用できることを明らかにしている。本年度は、同配位子のバリエーションを強化すべく、五員環CAFeC及びシクロペンタジエニル（Cp）基をペンタメチルシクロペンタジエニル（Cp*）基に置き換えた七員環CAFeCの開発を行った。
五員環CAFeC配位子前駆体となるイミニウム塩の合成は、プロトタイプ配位子の合成ルートをベースに行ったが、中間体が不安定な化学種であることが明らかになったため、若干のルート変更を行うことで実施した。得られたCAFeCの配位子としての電子的性質は、 CAFeCのイリジウムジカルボニル錯体を合成し、IR測定することで求めた。その結果、新たな配位子の配位力は、これまでのCAFeC同様に非常に強いことが分かった。
また、七員環Cp*-CAFeCに関しては昨年度の研究成果を基に、より完成度の高い配位子の開発を試みた。その結果、N原子上の置換基のバリエーションを強化することで、イミンの不斉水素移動反応において、より優れたエナンチオ選択性を発現する新たな不斉配位子を見出すことができた。

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

• [Journal Article] <i>N</i>-Heterocyclic Carbene Ligands Having Planar Chiral Ferrocene Structure (2020)
  • Author(s): Yoshida Kazuhiro、Yasue Risa
  • Journal Title: Journal of Synthetic Organic Chemistry, Japan Volume: 78 Issue: 1 Pages: 28-40
  • DOI: 10.5059/yukigoseikyokaishi.78.28
  • NAID: 130007783804
  • ISSN: 0037-9980, 1883-6526
  • Year and Date: 2020-01-01
  • Peer Reviewed
• [Journal Article] Synthesis of [1]benzothiopheno[2,3-b][1]benzothiophene derivatives through iodine-mediated sulfuration reaction of 1,1-diarylethylenes (2020)
  • Author(s): Sakai Shuta、Sato Kazuki、Yoshida Kazuhiro
  • Journal Title: Tetrahedron Letters Volume: 61 Issue: 6 Pages: 151476-151476
  • DOI: 10.1016/j.tetlet.2019.151476
  • Peer Reviewed
• [Journal Article] Development of Planar Chiral Five-Membered Cyclic (Amino)(ferrocenylene)carbene Ligand and Its Iridium Dicarbonyl Complex (2020)
  • Author(s): Takagaki Waka、Yasue Risa、Yoshida Kazuhiro
  • Journal Title: Bulletin of the Chemical Society of Japan Volume: 93 Issue: 2 Pages: 200-204
  • DOI: 10.1246/bcsj.20190325
  • NAID: 130007798365
  • Peer Reviewed
• [Journal Article] Synthesis and Application of Planar Chiral Cyclic (Amino)(ferrocenyl)carbene Ligands Bearing FeCp* Group (2019)
  • Author(s): Yasue Risa、Yoshida Kazuhiro
  • Journal Title: Organometallics Volume: 38 Issue: 9 Pages: 2211-2217
  • DOI: 10.1021/acs.organomet.9b00171
  • Peer Reviewed
• [Journal Article] Chiral Bicyclic NHC/Cu Complexes for Catalytic Asymmetric Borylation of α,β-Unsaturated Esters (2019)
  • Author(s): Miwa Yuya、Kamimura Takumi、Sato Kiyoaki、Shishido Daichi、Yoshida Kazuhiro
  • Journal Title: The Journal of Organic Chemistry Volume: 84 Issue: 21 Pages: 14291-14296
  • DOI: 10.1021/acs.joc.9b02096
  • Peer Reviewed
• [Journal Article] Versatile and Enantioselective Preparation of Planar-Chiral Metallocene-Fused 4-Dialkylaminopyridines and Their Application in Asymmetric Organocatalysis (2019)
  • Author(s): Yoshida Kazuhiro、Liu Qiang、Yasue Risa、Wada Shiro、Kimura Ryosuke、Konishi Takuma、Ogasawara Masamichi
  • Journal Title: ACS Catalysis Volume: 10 Issue: 1 Pages: 292-301
  • DOI: 10.1021/acscatal.9b04438
  • NAID: 120006937693
  • Peer Reviewed
• [Journal Article] Cover Feature: Planar‐Chiral Ferrocene‐Based N‐Heterocyclic Carbene Ligands (Chem. Eur. J. 70/2018) (2018)
  • Author(s): Yoshida Kazuhiro、Yasue Risa
  • Journal Title: Chemistry A European Journal Volume: 24 Issue: 70 Pages: 18565-18565
  • DOI: 10.1002/chem.201805458
• [Journal Article] Planar‐Chiral Ferrocene‐Based N‐Heterocyclic Carbene Ligands (2018)
  • Author(s): Yoshida Kazuhiro、Yasue Risa
  • Journal Title: Chemistry A European Journal Volume: 24 Issue: 70 Pages: 18575-18586
  • DOI: 10.1002/chem.201803903
  • Peer Reviewed
• [Presentation] Synthesis and Application of Planar Chiral Cyclic(amino)(ferrocenyl)carbene Bearing Cp* Group (2019)
  • Author(s): Yasue Risa、Yoshida Kazuhiro
  • Organizer: 20th IUPAC International Symposium on Organometallic Chemistry Directed Towards Organic Synthesis (OMCOS 20)
  • Int'l Joint Research
• [Presentation] Versatile and Enantiolselective Preparation of Planar-Chiral Metallocene-Fused 4-Dialkylaminopyridines and Their Application in Asymmetric Organocatalysis (2019)
  • Author(s): Yoshida Kazuhiro、Liu Qiang、Yasue Risa、Wada Shiro、Kimura Ryosuke、Konishi Takuma、Ogasawara Masamichi
  • Organizer: 4th International Symposium on Precisely Designed Catalysts with Customized Scaffolding
  • Int'l Joint Research
• [Presentation] Synthesis and Application of Planar Chiral Cyclic(amino)(ferrocenyl)carbene Ligands Bearing FeCp* (2019)
  • Author(s): Yasue Risa、Yoshida Kazuhiro
  • Organizer: 4th International Symposium on Precisely Designed Catalysts with Customized Scaffolding
  • Int'l Joint Research
• [Presentation] 面不斉アミノメタロセニルカルベン金属錯体触媒の開発 (2019)
  • Author(s): 吉田 和弘
  • Organizer: 新学術領域研究「精密制御反応場」 第6回公開シンポジウム
• [Presentation] Planar Chiral Cyclic Amino(ferrocenyl)carbene as Ligand for Transition Metals (2018)
  • Author(s): Risa Yasue, Yuta Shikata, Kazuhiro Yoshida
  • Organizer: Symposium on Molecular Chirality 2018
• [Presentation] 面性不斉五員環アミノフェロセニルカルベン配位子の開発 (2018)
  • Author(s): 高垣 和果、安江 里紗、四方 祐太、吉田 和弘
  • Organizer: 第75回有機合成化学協会関東支部シンポジウム
• [Presentation] Development of Planar Chiral N-Heterocyclic Carbene Ligands Bearing CoC4Ph4 Group (2018)
  • Author(s): Midori Kushima, Risa Yasue, Kazuhiro Yoshida
  • Organizer: 1st International Symposium of Soft Molecular Activation Research Center
• [Presentation] フェロセン縮環した面不斉環状ホスホン酸類の不斉合成 (2018)
  • Author(s): 劉 強、安江 里紗、岡崎 願之晋、吉田 和弘、小笠原 正道
  • Organizer: 第65回有機金属化学討論会
• [Presentation] Fe(C5Me5)基をもつ新規面性不斉NHC配位子の開発 (2018)
  • Author(s): 安江 里紗、四方 祐太、吉田 和弘
  • Organizer: 第65回有機金属化学討論会
• [Presentation] Versatile and Enantioselective Preparation of Planar-Chiral Metallocene-Fused 4-Dialkylaminopyridines and Their Application in Asymmetric Organocatalysis (2018)
  • Author(s): Kazuhiro Yoshida, Qiang Liu, Risa Yasue, Shiro Wada, Ryosuke Kimura, Masamichi Ogasawara
  • Organizer: The 14th International Kyoto Conference on New Aspects of Organic Chemistry
  • Int'l Joint Research
• [Presentation] Development of Planar Chiral (Amino)(ferrocenyl)carbene Ligand Having Cp*Fe Moiety (2018)
  • Author(s): Risa Yasue, Yuta Shikata, Kazuhiro Yoshida
  • Organizer: The 14th International Kyoto Conference on New Aspects of Organic Chemistry
  • Int'l Joint Research
• [Remarks] 面性不斉NHC配位子/金属錯体触媒の開発
  • URL: http://www.s.chiba-u.ac.jp/pr/files/News_46.pdf
• [Remarks] 面不斉アミノメタロセニルカルベン金属錯体触媒の開発
  • URL: http://precisely-designed-catalyst.jp/jpn/newsletter/pdf/NL_36.pdf