Structural modification of chiral organic ion-pair for the development of stereoselective catalytic transformations

• Project/Area Number: 23685018
• Research Category: Grant-in-Aid for Young Scientists (A)
• Allocation Type: Single-year Grants
• Research Field: Synthetic chemistry
• Research Institution: Nagoya University
• Principal Investigator: URAGUCHI Daisuke 名古屋大学, 工学(系)研究科(研究院), 准教授 (70426328)
• Project Period (FY): 2011-04-01 – 2015-03-31
• Project Status: Completed (Fiscal Year 2014)
• Budget Amount: ¥18,330,000 (Direct Cost: ¥14,100,000、Indirect Cost: ¥4,230,000); Fiscal Year 2014: ¥6,110,000 (Direct Cost: ¥4,700,000、Indirect Cost: ¥1,410,000); Fiscal Year 2013: ¥6,110,000 (Direct Cost: ¥4,700,000、Indirect Cost: ¥1,410,000); Fiscal Year 2012: ¥6,110,000 (Direct Cost: ¥4,700,000、Indirect Cost: ¥1,410,000)
• Keywords: 有機分子触媒 / 有機化学 / 不斉合成 / アンモニウムベタイン / 超分子イオン対 / キラル超分子イオン対

Outline of Final Research Achievements

This program was performed for the development of synergistic catalysis of an organic cation and an organic anion. Intermolecular ion-pairs such as chiral phosphonium aryloxide-arylhydroxide assemblies showed extraordinary high performance in a stereo- and regio-selective 1,6-addition reaction. On the other hand, intramolecular ion-pairs, chiral ammonium betaines, were found to be a key catalyst for accomplishing a series of highly stereoselective aza-Henry reactions of unsaturated nitroalkanes.

Research Products

• [Journal Article] Vinylogy in Nitronates: Utilization of α-Aryl Conjugated Nitroolefins as a Nucleophile for Highly Stereoselective Aza-Henry Reaction (2015)
  • Author(s): Keigo Oyaizu, Daisuke Uraguchi, Takashi Ooi
  • Journal Title: Chem. Commun. Volume: 51 Issue: 21 Pages: 4437-4439
  • DOI: 10.1039/c4cc10261d
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Chiral Ammonium Betaine-Catalyzed Highly Stereoselective Aza-Henry Reaction of α-Aryl Nitromethanes with Aromatic N-Boc Imines (2014)
  • Author(s): Daisuke Uraguchi, Keigo Oyaizu, Haruhiro Noguchi, Takashi Ooi
  • Journal Title: Chem. Asian J. Volume: 10 Issue: 2 Pages: 334-337
  • DOI: 10.1002/asia.201402943
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] The Practical Preparation of Chiral N-Sulfonyl Oxaziridines via Catalytic Asymmetric Payne Oxidation (2014)
  • Author(s): Ryosuke Tsutsumi, Seonwoo Kim, Daisuke Uraguchi, Takashi Ooi
  • Journal Title: Synthesis Volume: 46 Issue: 07 Pages: 871-878
  • DOI: 10.1055/s-0033-1340818
  • Peer Reviewed
• [Journal Article] 忘れられた反応剤Davis’オキサジリジン (2013)
  • Author(s): 浦口 大輔, 堤 亮祐, 大井 貴史
  • Journal Title: 月刊「化学」 Volume: 68 Pages: 66-67
• [Journal Article] Nitroolefins as a Nucleophilic Component for Highly Stereoselective Aza-Henry Reaction under the Catalysis of Chiral Ammonium Betaines (2012)
  • Author(s): Uraguchi, Daisuke; Oyaizu, Keigo; Ooi, Takashi
  • Journal Title: Chem. Eur. J. Volume: 18 Issue: 27 Pages: 8306-8309
  • DOI: 10.1002/chem.201201259
  • Peer Reviewed
• [Journal Article] Ionic Nucleophilic Catalysis of Chiral Ammonium Betaines for Highly Stereoselective Aldol Reaction from Oxindole-Derived Vinylic Carbonates (2012)
  • Author(s): Uraguchi, Daisuke; Koshimoto, Kyohei; Ooi, Takashi
  • Journal Title: J. Am. Chem. Soc. Volume: 134 Issue: 16 Pages: 6972-6975
  • DOI: 10.1021/ja3022939
  • Peer Reviewed
• [Journal Article] Highly Stereoselective Catalytic Conjugate Addition of Acyl Anion Equivalent to Nitroolefins (2012)
  • Author(s): 浦口大輔、上木佑介、大井貴史
  • Journal Title: Chem.Sci. Volume: 3 Issue: 3 Pages: 842-845
  • DOI: 10.1039/c1sc00678a
  • Peer Reviewed
• [Journal Article] Base-Catalyzed Direct Aldolization of α-Alkyl-α-Hydroxy Trialkyl Phosphonoacetates (2012)
  • Author(s): Corbett, Michael; Uraguchi, Daisuke; Ooi, Takashi; Johnson, Jeffrey
  • Journal Title: Angew.Chem.Int.Ed. Volume: 51(印刷中)(in press) Issue: 19 Pages: 4685-4689
  • DOI: 10.1002/anie.201200559
  • Peer Reviewed
• [Presentation] Catalysis of Chiral Aminophosphonium Salts (2015)
  • Author(s): 浦口大輔
  • Organizer: Lectureship Award MBLA 10th Anniversary Special Lectures
  • Place of Presentation: 日本大学（船橋キャンパス）
  • Year and Date: 2015-03-29
  • Invited
• [Presentation] Molecular Design and Application of a New Brønsted Acid Possessing Hexacoordinating Chiral Phosphate (2015)
  • Author(s): Takaki Ito, Daisuke Uraguchi, Takashi, Ooi
  • Organizer: 日本化学会第95 春季年会
  • Place of Presentation: 日本大学（船橋キャンパス）
  • Year and Date: 2015-03-26 – 2015-03-29
• [Presentation] Strategy for Vinylogous Nitronate Generation: Application to Highly Stereoselective Aza-Henry Reaction (2015)
  • Author(s): Keigo Oyaizu, Daisuke Uraguchi, Takashi Ooi
  • Organizer: 日本化学会第95 春季年会
  • Place of Presentation: 日本大学（船橋キャンパス）
  • Year and Date: 2015-03-26 – 2015-03-29
• [Presentation] Betaine-Type Electron-Transfer Catalyst: Design and Application (2015)
  • Author(s): Torii Masahiro, Daisuke Uraguchi, Takashi Ooi
  • Organizer: 日本化学会第95 春季年会
  • Place of Presentation: 日本大学（船橋キャンパス）
  • Year and Date: 2015-03-26
• [Presentation] キラル有機イオン対触媒の創製と機能創出 (2014)
  • Author(s): 浦口大輔
  • Organizer: 第24回 万有福岡シンポジウム グリーンサスティナブルケミストリーを指向した有機合成－有機合成が世界を救う
  • Place of Presentation: 九州大学
  • Year and Date: 2014-06-07
  • Invited
• [Presentation] キラル超分子イオン対触媒による高位置・高立体選択的1,6-付加反応の開発 (2014)
  • Author(s): 吉岡 謙, 浦口 大輔, 大井 貴史
  • Organizer: 日本化学会第94 春季年会
  • Place of Presentation: 名古屋大学
• [Presentation] ベタイン型エノラートを鍵中間体とする分子変換 (2014)
  • Author(s): 鳥居 雅弘, 浦口 大輔, 大井 貴史
  • Organizer: 日本化学会第94 春季年会
  • Place of Presentation: 名古屋大学
• [Presentation] Diastereodivergent Catalysis of Chiral Aminophosphonium Aryloxides for Highly Regio- and Stereoselective 1,6-Addition to δ-Aryl Dienyl N-Acylpyrroles (2013)
  • Author(s): Ken Yoshioka, Daisuke Uraguchi, Takashi Ooi
  • Organizer: 第10回カルバニオン化学国際シンポジウム（ISCC-10）
  • Place of Presentation: 京都
• [Presentation] Highly Regio-, Diastereo-, and Enantioselective Vinylogous Michael Reaction (2012)
  • Author(s): Ken Yoshioka, Yusuke Ueki, Daisuke Uraguchi, Takashi Ooi
  • Organizer: IKCOC-12
  • Place of Presentation: 京都
• [Presentation] キラルアミノホスホニウムバフェートを触媒とするニトロエナインへの不斉アザ共役付加反応 (2012)
  • Author(s): 木津 智仁, 木下 奈津子, 浦口 大輔, 大井 貴史
  • Organizer: 第43回 中部化学関係学協会支部連合秋季大会
  • Place of Presentation: 名古屋
• [Presentation] アニオン認識型キラルオニウム塩の創製と触媒的不斉合成への応用 (2012)
  • Author(s): 浦口 大輔
  • Organizer: 日本化学会第92 春季年会
  • Place of Presentation: 東京
  • Invited
• [Presentation] キラルアンモニウムベタインを触媒とする不斉アザHenry反応 (2012)
  • Author(s): 小栁津 圭吾, 野口 晴大, 浦口 大輔, 大井 貴史
  • Organizer: 日本化学会第92 春季年会
  • Place of Presentation: 東京
• [Presentation] ビニリックカーボネートをエノラート前駆体とする高立体選択的アルドール型反応の開発 (2012)
  • Author(s): 越本 恭平, 浦口 大輔, 大井 貴史
  • Organizer: 日本化学会第92 春季年会
  • Place of Presentation: 東京
• [Presentation] Precise Structural Control of Spontaneous Molecular Assembly of Chiral Tetraaminophosphonium Aryloxide-Arylhydroxide(s) (2011)
  • Author(s): Yusuke Ueki, Daisuke Uraguchi, Takashi Ooi
  • Organizer: Nagoya University Global COE International Symposium on on Elucidation and Design of Materials and Molecular Functions & 7th and 8th Yoshimasa Hirata Memorial Lecture
  • Place of Presentation: 名古屋
• [Presentation] アシルアニオン等価体のニトロオレフィンへの共役付加反応 (2011)
  • Author(s): 上木 佑介, 浦口 大輔, 大井 貴史
  • Organizer: 第5回物質科学フロンティアセミナー「新時代の物質創製を目指して ―光、金属、生命を操る―」
  • Place of Presentation: 名古屋
• [Presentation] ビニロガスニトロナートを経る高立体選択的Aza-Henry反応の開発 (2011)
  • Author(s): 小栁津 圭吾, 浦口 大輔, 大井 貴史
  • Organizer: 第42回中部化学関係学協会支部連合秋季大会
  • Place of Presentation: 長野
• [Presentation] アンモニウムベタインをイオン性求核触媒とする不斉Steglich反応の開発 (2011)
  • Author(s): 越本 恭平, 三宅 修平, 浦口 大輔, 大井 貴史
  • Organizer: 第28回 有機合成化学セミナー
  • Place of Presentation: 天童
• [Presentation] 求核剤としてのニトロオレフィン－高立体選択的Aza-Henry反応 (2011)
  • Author(s): 小栁津 圭吾, 浦口 大輔, 大井 貴史
  • Organizer: 第28回 有機合成化学セミナー
  • Place of Presentation: 天童