Asymmetric construction of a stereogenic carbon center substituted with aryl groups

• Project/Area Number: 24550117
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Multi-year Fund
• Section: 一般
• Research Field: Synthetic chemistry
• Research Institution: Kyoto University
• Principal Investigator: NISHIMURA Takahiro 京都大学, 理学(系)研究科(研究院), 講師 (50335197)
• Research Collaborator: EBE Yusuke ; NAGAMOTO Midori ; TAKECHI Ryosuke ; HATANO Miyuki ; YAMAUCHI Daisuke ; NAGAI Tomotaka ; FUJIMOTO Hiroto ; NOISHIKI Akira ; TAKIGUCHI Yuka ; MAEDA Yuko ; ASHOURI Akram
• Project Period (FY): 2012-04-01 – 2015-03-31
• Project Status: Completed (Fiscal Year 2014)
• Budget Amount: ¥5,590,000 (Direct Cost: ¥4,300,000、Indirect Cost: ¥1,290,000); Fiscal Year 2014: ¥1,560,000 (Direct Cost: ¥1,200,000、Indirect Cost: ¥360,000); Fiscal Year 2013: ¥1,690,000 (Direct Cost: ¥1,300,000、Indirect Cost: ¥390,000); Fiscal Year 2012: ¥2,340,000 (Direct Cost: ¥1,800,000、Indirect Cost: ¥540,000)
• Keywords: 不斉合成 / 触媒反応 / ロジウム / アリールボロン酸 / イリジウム / 金属触媒 / アリール化 / イミン / アミノ酸 / 不斉付加 / 触媒 / 不斉４置換炭素 / アミン / 付加反応

Outline of Final Research Achievements

We have developed Rh-catalyzed arylation methods by use of arylboron reagents for the synthesis of chiral compounds having a stereogenic carbon center that is substituted with aryl groups. The use of chiral diene ligands base on a tetrafluorobenzobarrelene (tfb) framework was found to be effective in catalyzing the arylation reaction with high enantioselectivity. It was also found that Ir-catalyzed annulation of aromatic imines with 1,3-dienes or alkynes proceeds via C-H bond activation with high stereoselectivity.

Research Products

• [Journal Article] Enantioselective 1,4-addition of cyclopropylboronic acid catalyzed by rhodium/chiral diene complexes (2015)
  • Author(s): Ryosuke Takechi, Takahiro Nishimura
  • Journal Title: Chemical Communications Volume: 印刷中 Issue: 40 Pages: 8528-8531
  • DOI: 10.1039/c5cc02140e
  • Peer Reviewed / Open Access / Acknowledgement Compliant
• [Journal Article] Rhodium-catalyzed asymmetric addition of arylboronic acids to cyclic N-sulfonyl ketimines towards the synthesis of α,α-diaryl-α-amino acid derivatives (2015)
  • Author(s): Ryosuke Takechi, Takahiro Nishimura
  • Journal Title: Organic & Biomolecular Chemistry Volume: 13 Issue: 17 Pages: 4918-4924
  • DOI: 10.1039/c5ob00431d
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Iridium-Catalyzed Annulation of Aromatic Imines with 1,3-Dienes via Direct Functionalization of an Aromatic C―H Bond (2015)
  • Author(s): Yusuke Ebe, Miyuki Hatano and Takahiro Nishimura
  • Journal Title: Advanced Synthesis & Catalysis Volume: 印刷中 Issue: 7 Pages: 1425-1436
  • DOI: 10.1002/adsc.201401171
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Iridium-Catalyzed Annulation of Salicylimines with 1,3-Dienes (2014)
  • Author(s): Yusuke Ebe and Takahiro Nishimura
  • Journal Title: Journal of the American Chemical Society Volume: 135 Issue: 26 Pages: 9284-9287
  • DOI: 10.1021/ja504990a
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Catalytic [3 + 2] annulation of ketimines with alkynes via C-H activation by a cationic iridium(cod) complex (2014)
  • Author(s): Midori Nagamoto, Takahiro Nishimura
  • Journal Title: Chemical Communications Volume: 50 Issue: 47 Pages: 6274-6277
  • DOI: 10.1039/c4cc01874e
  • Peer Reviewed
• [Journal Article] Asymmetric synthesis of gem-diaryl substituted cyclic sulfamidates and sulfamides by rhodium-catalyzed arylation of cyclic ketimines (2013)
  • Author(s): Takahiro Nishimura, Yusuke Ebe, Hiroto Fujimoto, Tamio Hayashi
  • Journal Title: Chemical Communications Volume: 49 Issue: 48 Pages: 5504-5506
  • DOI: 10.1039/c3cc42071j
  • Peer Reviewed
• [Journal Article] Enantioselective [3 + 2] annulation via C-H activation between cyclic N-acyl ketimines and 1,3-dienes catalyzed by iridium/chiral diene complexes (2013)
  • Author(s): Takahiro Nishimura, Midori Nagamoto, Yusuke Ebe, Tamio Hayashi
  • Journal Title: Chemical Science Volume: 4 Issue: 12 Pages: 4499-4504
  • DOI: 10.1039/c3sc52379a
  • Peer Reviewed
• [Journal Article] Iridium-Catalyzed [3 + 2] Annulation of Cyclic N‐Sulfonyl Ketimines with 1,3-Dienes via C－H Activation (2013)
  • Author(s): Takahiro Nishimura, Yusuke Ebe, Tamio Hayashi
  • Journal Title: Journal of the American Chemical Society Volume: 135 Issue: 6 Pages: 2092-2095
  • DOI: 10.1021/ja311968d
  • Peer Reviewed
• [Journal Article] Hydroxorhodium/Chiral Diene Complexes as Effective Catalysts for the Asymmetric Arylation of 3-Aryl-3-hydroxyisoindolin-1-ones (2013)
  • Author(s): Takahiro Nishimura, Akira Noishiki, Yusuke Ebe, Tamio Hayashi
  • Journal Title: Angewandte Chemie, International Edition Volume: 52 Issue: 6 Pages: 1777-1780
  • DOI: 10.1002/anie.201208593
  • Peer Reviewed
• [Journal Article] Rhodium/chiral diene-catalyzed asymmetric methylation of N-sulfonylarylimines with trimethylboroxine (2012)
  • Author(s): Takahiro Nishimura, Akram Ashouri, Yusuke Ebe, Yuko Maeda, Tamio Hayashi
  • Journal Title: Tetrahedron: Asymmetry Volume: 23 Issue: 9 Pages: 655-658
  • DOI: 10.1016/j.tetasy.2012.04.021
  • Peer Reviewed
• [Journal Article] Effect of Chiral Diene Ligands in Rhodium-Catalyzed Asymmetric Addition of Arylboronic Acids to α,β-Unsaturated Sulfonyl Compounds (2012)
  • Author(s): Takahiro Nishimura, Yuka Takiguchi, Tamio Hayashi
  • Journal Title: Journal of the American Chemical Society Volume: 134 Issue: 22 Pages: 9086-9086
  • DOI: 10.1021/ja303109q
  • Peer Reviewed
• [Presentation] Iridium-Catalyzed Hydroarylation of Vinyl Ethers via C-H Bond Activation (2015)
  • Author(s): EBE, Yusuke; NISHIMURA, Takahiro
  • Organizer: 日本化学会第９５春期年会
  • Place of Presentation: 日本大学 理工学部船橋キャンパス／薬学部 （千葉県船橋市）
  • Year and Date: 2015-03-28
• [Presentation] Iridium-Catalyzed Asymmetric Intramolecular Hydrocarboxylation and Hydroimidation of Alkenes (2015)
  • Author(s): NAGAMOTO, Midori; NISHIMURA, Takahiro
  • Organizer: 日本化学会第９５春期年会
  • Place of Presentation: 日本大学 理工学部船橋キャンパス／薬学部 （千葉県船橋市）
  • Year and Date: 2015-03-28
• [Presentation] L1 正則化を用いた不斉触媒反応の定量的構造活性相関モデル構築 (2015)
  • Author(s): 山口 滋，西村貴洋，佐藤啓文
  • Organizer: 日本化学会第９５春期年会
  • Place of Presentation: 日本大学 理工学部船橋キャンパス／薬学部 （千葉県船橋市）
  • Year and Date: 2015-03-27
• [Presentation] ロジウム触媒を用いたアルジミンへのシクロプロピルボロキシンの不斉付加反応 (2015)
  • Author(s): 永井智隆，竹知亮輔，江邉裕祐，西村貴洋
  • Organizer: 日本化学会第９５春期年会
  • Place of Presentation: 日本大学 理工学部船橋キャンパス／薬学部 （千葉県船橋市）
  • Year and Date: 2015-03-27
• [Presentation] イリジウム触媒を用いたα-オキソカルボキシアミドと 1,3-ジエンとの不斉[3 + 2]環化反応 (2015)
  • Author(s): 幡野 幸，西村貴洋
  • Organizer: 日本化学会第９５春期年会
  • Place of Presentation: 日本大学 理工学部船橋キャンパス／薬学部 （千葉県船橋市）
  • Year and Date: 2015-03-26
• [Presentation] カチオン性イリジウム触媒を用いた C-H 活性化を経る芳香族ケチミンとアルキンとの不斉[3 + 2]環化反応 (2015)
  • Author(s): 山内大輔，永本 翠，西村 貴洋
  • Organizer: 日本化学会第９５春期年会
  • Place of Presentation: 日本大学 理工学部船橋キャンパス／薬学部 （千葉県船橋市）
  • Year and Date: 2015-03-26
• [Presentation] 9族遷移金属を使った触媒的不斉合成反応
  • Author(s): 西村貴洋
  • Organizer: 第48回天然物化学談話会
  • Place of Presentation: 大津
  • Invited
• [Presentation] ロジウム触媒を用いたケチミンのアリール化反応によるα-アミノ酸誘導体の不斉合成
  • Author(s): 竹知亮輔、西村貴洋
  • Organizer: 日本化学会第94春季年会
  • Place of Presentation: 名古屋
• [Presentation] イリジウム触媒を用いたC-H活性化を経るアリール置換Nスルホニルケチミンと1,3-ジエンとの[3 + 2]環化反応
  • Author(s): 西村貴洋，江邊裕祐，林 民生
  • Organizer: 日本化学会第93春期年会
  • Place of Presentation: 立命館大学（滋賀県）
• [Presentation] イリジウム触媒を用いたC-H活性化を経る3-アリール-3-ヒドロキシイソインドリン-1-オンと1,3-ジエンとの不斉[3 + 2]環化反応
  • Author(s): 西村貴洋，永本 翠，林 民生
  • Organizer: 日本化学会第93春期年会
  • Place of Presentation: 立命館大学（滋賀県）
• [Presentation] ロジウム触媒を用いた環状ケチミンの不斉アリール化反応
  • Author(s): 西村貴洋，藤本寛人，江邊裕祐，林 民生
  • Organizer: 日本化学会第93春期年会
  • Place of Presentation: 立命館大学（滋賀県）
• [Remarks]
  • URL: http://kuchem.kyoto-u.ac.jp/orgchem/OrgChem_Lab/Top.html
• [Remarks] 京都大学大学院理学研究科化学専攻有機化学研究室
  • URL: http://kuchem.kyoto-u.ac.jp/orgchem/OrgChem_Lab/Top.html