Practical Synthesis of Asymmetric Pyridine Catalysts Using Ring-closing Approach

• Project/Area Number: 15K05494
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Multi-year Fund
• Section: 一般
• Research Field: Synthetic chemistry
• Research Institution: Chiba University
• Principal Investigator: YOSHIDA Kazuhiro 千葉大学, 大学院理学研究院, 准教授 (60375607)
• Project Period (FY): 2015-04-01 – 2018-03-31
• Project Status: Completed (Fiscal Year 2017)
• Budget Amount: ¥5,070,000 (Direct Cost: ¥3,900,000、Indirect Cost: ¥1,170,000); Fiscal Year 2017: ¥1,690,000 (Direct Cost: ¥1,300,000、Indirect Cost: ¥390,000); Fiscal Year 2016: ¥1,690,000 (Direct Cost: ¥1,300,000、Indirect Cost: ¥390,000); Fiscal Year 2015: ¥1,690,000 (Direct Cost: ¥1,300,000、Indirect Cost: ¥390,000)
• Keywords: ピリジン環 / 面不斉 / フェロセン / 閉環反応

Outline of Final Research Achievements

The newly developed method of preparing planar-chiral metallocene-fused 4-dialkylaminopyridine derivatives is versatile and introduction of a wide range of substituents is possible. By this method, previously unknown various planar-chiral pyridine derivatives are prepared in enantiomerically pure forms.

Research Products

• [Journal Article] Coordination Behavior of a Planar Chiral Cyclic (Amino)(Ferrocenyl)Carbene Ligand in Iridium Complexes (2017)
  • Author(s): Shikata Yuta、Yasue Risa、Yoshida Kazuhiro
  • Journal Title: Chem. Eur. J. Volume: 23 Issue: 66 Pages: 16806-16812
  • DOI: 10.1002/chem.201703467
  • Peer Reviewed
• [Journal Article] A planar chiral six-membered cyclic (amino)(ferrocenyl)carbene and its sulfur adduct (2017)
  • Author(s): Yasue Risa、Miyauchi Masaru、Yoshida Kazuhiro
  • Journal Title: Tetrahedron: Asymmetry Volume: 28 Issue: 6 Pages: 824-829
  • DOI: 10.1016/j.tetasy.2017.05.004
  • Peer Reviewed
• [Journal Article] Synthesis of o-Allyloxyethynylbenzene Derivatives via Cu-Catalyzed Suzuki-Miyaura-Type Reaction and Their Transformations for Heterocyclic Compounds (2017)
  • Author(s): Kohei Watanabe, Takashi Mino, Eri Ishikawa, Miyu Okano, Tatsuya Ikematsu, asushi Yoshida, Masami Sakamoto,Kazuki Sato and Kazuhiro Yoshida
  • Journal Title: Eur. J. Org. Chem. Volume: 2017 Issue: 16 Pages: 2359-2368
  • DOI: 10.1002/ejoc.201700217
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Planar Chiral Cyclic (Amino)(ferrocenyl)carbene as Ligand for Transition Metals (2017)
  • Author(s): Risa Yasue, Masaru Miyauchi, Kazuhiro Yoshida
  • Journal Title: Adv. Synth. Catal. Volume: 359 Issue: 2 Pages: 255-259
  • DOI: 10.1002/adsc.201600999
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Enantioselective Synthesis of Ferrocene- or Cymantrene-Fused Planar-Chiral Phospholes (2017)
  • Author(s): Hu, H.; Wu, W.-Y.; Takahashi, T.; Yoshida, K.; Ogasawara, M.
  • Journal Title: Eur. J. Inorg. Chem. Volume: - Issue: 2 Pages: 325-329
  • DOI: 10.1002/ejic.201600875
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Enantioselective Nitroso Aldol Reaction Catalyzed by Chiral Phosphine-Silver Complex (2016)
  • Author(s): Akira Yanagisawa, Yuqin Lin, Akihiro Takeishi, Kazuhiro Yoshida
  • Journal Title: Eur. J. Org. Chem. Volume: 32 Issue: 32 Pages: 5355-5359
  • DOI: 10.1002/ejoc.201601143
  • Peer Reviewed
• [Journal Article] Enantio- and Diastereoselective Cross-annulation of Enal and Ketone with New Chiral Bicyclic <i>N</i>-Heterocyclic Carbene Catalysts (2016)
  • Author(s): Momo Hasegawa, Kazuhiro Yoshida, Akira Yanagisawa
  • Journal Title: Chemistry Letters Volume: 45 Issue: 3 Pages: 294-296
  • DOI: 10.1246/cl.151116
  • NAID: 130005132185
  • ISSN: 0366-7022, 1348-0715
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Chiral Bicyclic NHC/Ir Complexes for Catalytic Asymmetric Transfer Hydrogenation of Ketones (2015)
  • Author(s): Kazuhiro Yoshida, Takumi Kamimura, Hiroshi Kuwabara, Akira Yanagisawa
  • Journal Title: Chem. Commun. Volume: 51 Issue: 84 Pages: 15442-15445
  • DOI: 10.1039/c5cc05318h
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Enantioselective Synthesis of Planar-Chiral Ferrocene-Fused 4-Pyridones and Their Application in Construction of Pyridine-Based Organocatalyst Library (2015)
  • Author(s): Masamichi Ogasawara, Shiro Wada, Erika Isshiki, Takumi Kamimura, Akira Yanagisawa, Tamotsu Takahashi, Kazuhiro Yoshida
  • Journal Title: Org. Lett. Volume: 17 Issue: 9 Pages: 2286-2289
  • DOI: 10.1021/acs.orglett.5b01044
  • Peer Reviewed / Acknowledgement Compliant
• [Presentation] Coordination Behavior of a Planar Chiral Cyclic (Amino)(Ferrocenyl)Carbene in Iridium Complexes (2018)
  • Author(s): Yuta Shikata, Risa Yasue, Kazuhiro Yoshida
  • Organizer: The Second Symposium of Chiral Molecular Science and Technology in Chiba University-Advanced Materials Science, Biology & Nanophotonics in Chiba-
  • Int'l Joint Research
• [Presentation] キラル二環性NHC金属錯体触媒の開発 (2018)
  • Author(s): 吉田 和弘
  • Organizer: スパイラル融合による有機材料の創製 スタートアップ・シンポジウム
• [Presentation] 面性不斉環状アミノフェロセニルカルベン金属錯体触媒の開発 (2018)
  • Author(s): 吉田 和弘
  • Organizer: 新技術説明会
• [Presentation] CoC4Ph4基を有する面性不斉N-ヘテロサイクリックカルベン配位子の開発 (2018)
  • Author(s): 櫛間 翠、安江 里紗、吉田 和弘
  • Organizer: 日本化学会第98春季年会
• [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、四方 祐太、吉田 和弘
  • Organizer: 日本化学会第98春季年会
• [Presentation] キラル二環性NHC-ホスフィンイリジウム錯体の開発と不斉水素移動反応への応用 (2018)
  • Author(s): 宍戸 大智、吉田 和弘
  • Organizer: 日本化学会第98春季年会
• [Presentation] 面性不斉七員環アミノフェロセニルカルベン配位子の立体および電子的性質 (2018)
  • Author(s): 四方 祐太、安江 里紗、吉田 和弘
  • Organizer: 日本化学会第98春季年会
• [Presentation] FeCp*基を有する面性不斉N-ヘテロサイクリックカルベン配位子の開発 (2018)
  • Author(s): 安江 里紗、四方 祐太、吉田 和弘
  • Organizer: 日本化学会第98春季年会
• [Presentation] メタロセン縮環不斉4-ジアルキルアミノピリジン誘導体のエナンチオ選択的合成法の開発と応用 (1) (2017)
  • Author(s): 木村 亮介、劉 強、和田 志郎、小笠原 正道、吉田 和弘
  • Organizer: 日本化学会第97春季年会
  • Place of Presentation: 慶應義塾大学（東京都・千代田区）
  • Year and Date: 2017-03-16
• [Presentation] メタロセン縮環不斉4-ジアルキルアミノピリジン誘導体のエナンチオ選択的合成法の開発と応用 (2) (2017)
  • Author(s): 劉 強、木村 亮介、和田 志郎、吉田 和弘、小笠原 正道
  • Organizer: 日本化学会第97春季年会
  • Place of Presentation: 慶應義塾大学（東京都・千代田区）
  • Year and Date: 2017-03-16
• [Presentation] ドミノ酸化/分子内環化反応を用いる含窒素縮合環の形成 (2017)
  • Author(s): 植田 潤一、小笠原 正道、吉田 和弘
  • Organizer: 日本化学会第97春季年会
  • Place of Presentation: 慶應義塾大学（東京都・千代田区）
  • Year and Date: 2017-03-16
• [Presentation] ヨウ素を活用するベンゾチオフェンおよびベンゾチエノベンゾチオフェンの合成 (2017)
  • Author(s): 佐藤 一樹、吉田 和弘
  • Organizer: 日本化学会第97春季年会
  • Place of Presentation: 慶應義塾大学（東京都・千代田区）
  • Year and Date: 2017-03-16
• [Presentation] キラル二環性NHC銅錯体の開発と不斉触媒反応への応用 (2017)
  • Author(s): 佐藤 清晃、上村 拓未、吉田 和弘
  • Organizer: 日本化学会第97春季年会
  • Place of Presentation: 慶應義塾大学（東京都・千代田区）
  • Year and Date: 2017-03-16
• [Presentation] 面性不斉六員環アミノフェロセニルカルベン配位子の開発 (2017)
  • Author(s): 宮内 大、安江 里紗、吉田 和弘
  • Organizer: 日本化学会第97春季年会
  • Place of Presentation: 慶應義塾大学（東京都・千代田区）
  • Year and Date: 2017-03-16
• [Presentation] 面性不斉七員環アミノフェロセニルカルベン銅錯体触媒の開発 (2017)
  • Author(s): 安江 里紗、宮内 大、吉田 和弘
  • Organizer: 日本化学会第97春季年会
  • Place of Presentation: 慶應義塾大学（東京都・千代田区）
  • Year and Date: 2017-03-16
• [Presentation] 面性不斉七員環アミノフェロセニルカルベン銅錯体のトランスメタル化反応 (2017)
  • Author(s): 四方 祐太、安江 里紗、吉田 和弘
  • Organizer: 日本化学会第97春季年会
  • Place of Presentation: 慶應義塾大学（東京都・千代田区）
  • Year and Date: 2017-03-16
• [Presentation] Planar Chiral Six‐Membered Cyclic (Amino)(ferrocenyl)carbenes (2017)
  • Author(s): Masaru Miyauchi, Risa Yasue, Kazuhiro Yoshida
  • Organizer: The Second Symposium of Chiral Materials Science 2017
  • Place of Presentation: 千葉大学（千葉県・千葉市）
  • Year and Date: 2017-03-08
  • Int'l Joint Research
• [Presentation] 面性不斉六員環アミノフェロセニルカルベンとその硫黄付加体の合成 (2017)
  • Author(s): 安江 里紗、宮内 大、吉田 和弘
  • Organizer: 第64回有機金属化学討論会
• [Presentation] 面性不斉七員環アミノフェロセニルカルベン配位子が配位したイリジウム錯体の合成 (2017)
  • Author(s): 四方 祐太、安江 里紗、吉田 和弘
  • Organizer: 第64回有機金属化学討論会
• [Presentation] メタロセン縮環面不斉4-ピリドンおよび4-ジアルキルアミノピリジン類のエナンチオ選択的合成法の開発と不斉反応への応用 (2017)
  • Author(s): 劉 強、和田 志郎、木村 亮介、安江 里紗、吉田 和弘、小笠原 正道
  • Organizer: 第64回有機金属化学討論会
• [Presentation] Enantioselective Synthesis of Metallocene-Fused Planar-Chiral 4-Dialkylaminopyridine Derivatives and Their Applications (2016)
  • Author(s): Ryosuke Kimura, Qiang Liu, Shiro Wada, Masamichi Ogasawara, Kazuhiro Yoshida
  • Organizer: 2nd Joint Workshop on Chirality in Chiba University (WCCU) and Soft Molecule Activation (SMA)
  • Place of Presentation: 千葉大学（千葉県・千葉市）
  • Year and Date: 2016-12-19
  • Int'l Joint Research
• [Presentation] Development of Planar Chiral Six-Membered Cyclic (Amino)(ferrocenyl)carbene Ligands (2016)
  • Author(s): Masaru Miyauchi, Risa Yasue, Kazuhiro Yoshida
  • Organizer: 2nd Joint Workshop on Chirality in Chiba University (WCCU) and Soft Molecule Activation (SMA)
  • Place of Presentation: 千葉大学（千葉県・千葉市）
  • Year and Date: 2016-12-19
  • Int'l Joint Research
• [Presentation] 面性不斉環状アミノフェロセニルカルベン前駆体のモジュール合成 (2016)
  • Author(s): 安江 里紗、宮内 大、吉田 和弘
  • Organizer: 第63回有機金属化学討論会
  • Place of Presentation: 早稲田大学（東京都・新宿区）
  • Year and Date: 2016-09-14
• [Presentation] メタロセン縮環した面不斉ホスホールの不斉合成 (2016)
  • Author(s): 小笠原 正道、Hu Hao、Wu Wei-Yi、吉田 和弘、高橋 保
  • Organizer: 第63回有機金属化学討論会
  • Place of Presentation: 早稲田大学（東京都・新宿区）
  • Year and Date: 2016-09-14
• [Presentation] Synthesis of Substituted Aromatic Compounds Using Ruthenium-Catalyzed Ring-Closing Metathesis (2016)
  • Author(s): Kazuhiro Yoshida
  • Organizer: Joint Symposium on Chemistry between National University of Singapore and Chiba University
  • Place of Presentation: 千葉大学（千葉県千葉市）
  • Year and Date: 2016-03-28
  • Int'l Joint Research
• [Presentation] Ring-Closing Metathesis for the Synthesis of Aromatic Compounds (2016)
  • Author(s): Kazuhiro Yoshida
  • Organizer: The Joint Workshop on Chirality in Chiba University (WCCU) and Soft Molecule Activation (SMA)
  • Place of Presentation: 千葉大学（千葉県千葉市）
  • Year and Date: 2016-03-17
  • Int'l Joint Research
• [Presentation] Enantio- and Diastereoselective Cross-Annulation of an Enal and a Ketone with New Chiral Bicyclic N-Heterocyclic Carbene Catalysts (2016)
  • Author(s): Momo Hasegawa, Kazuhiro Yoshida, Akira Yanagisawa
  • Organizer: The Joint Workshop on Chirality in Chiba University (WCCU) and Soft Molecule Activation (SMA)
  • Place of Presentation: 千葉大学（千葉県千葉市）
  • Year and Date: 2016-03-17
  • Int'l Joint Research
• [Presentation] Chiral Bicyclic NHC/Ir Complexes for Catalytic Asymmetric Transfer Hydrogenation of Ketones (2016)
  • Author(s): Takumi Kamimura, Hiroshi Kuwabara, Kazuhiro Yoshida, Akira Yanagisawa
  • Organizer: The First Symposium of Chiral Molecular Science and Technology in Chiba University
  • Place of Presentation: 千葉大学（千葉県千葉市）
  • Year and Date: 2016-02-29
  • Int'l Joint Research
• [Presentation] Synthesis of Substituted Aromatic Compounds Using Ruthenium-Catalyzed Ring-Closing Metathesis (2015)
  • Author(s): Kazuhiro Yoshida
  • Organizer: The 6th Japanese-Sino Symposium on Organic Chemistry for Young Scientists
  • Place of Presentation: 秋保リゾートホテルクレセント（宮城県仙台市）
  • Year and Date: 2015-09-06
  • Int'l Joint Research / Invited
• [Remarks] 研究室ホームページ
  • URL: http://tmco.chem.chiba-u.jp
• [Patent(Industrial Property Rights)] 面性不斉メタロセン縮環カルベン及びその製造方法、並びに該誘導体を配位子とする金属錯体 (2016)
  • Inventor(s): 吉田和弘、安江里紗、宮内大、四方祐太
  • Industrial Property Rights Holder: 千葉大学
  • Industrial Property Rights Type: 特許
  • Industrial Property Number: 2016-166374
  • Filing Date: 2016-08-29
• [Patent(Industrial Property Rights)] ４－ピリドンおよびその製造方法 (2015)
  • Inventor(s): 吉田和弘、小笠原正道、和田志郎、劉強、木村亮介
  • Industrial Property Rights Holder: 千葉大学
  • Industrial Property Rights Type: 特許
  • Industrial Property Number: 2015-206798
  • Filing Date: 2015-10-20