Challenge to asymmetric ester hydrolysis with artificial catalysts

• Project/Area Number: 23655087
• Research Category: Grant-in-Aid for Challenging Exploratory Research
• Allocation Type: Multi-year Fund
• Research Field: Synthetic chemistry
• Research Institution: Kyushu University
• Principal Investigator: TOKUNAGA Makoto 九州大学, 大学院・理学研究院, 教授 (40301767)
• Project Period (FY): 2011 – 2012
• Project Status: Completed (Fiscal Year 2012)
• Budget Amount: ¥3,900,000 (Direct Cost: ¥3,000,000、Indirect Cost: ¥900,000); Fiscal Year 2012: ¥1,820,000 (Direct Cost: ¥1,400,000、Indirect Cost: ¥420,000); Fiscal Year 2011: ¥2,080,000 (Direct Cost: ¥1,600,000、Indirect Cost: ¥480,000)
• Keywords: 選択的合成 / 不斉合成 / 有機分子触媒 / エステル / 不斉加水分解 / キラル相間移動触媒 / ２－アリールプロパン酸エステル類 / エノールエステル / アミノ酸 / 相間移動触媒 / 四級アンモニウム塩

Research Abstract

Asymmetric hydrolysis of alkenyl esters and simple esters have achieved with chiral quaternary ammonium salts as phase-transfer catalysts. Maximum selectivity was 95% ee for alkenyl esters and 85% ee for simple esters, respectively. In the case of alkenyl esters, enantio-differentiation was protonation step of enolates.

Research Products

• [Journal Article] Hydrolytic Enantioselective Protonation of Dienyl Esters and a Racemic β-Diketone with Chiral Phase-Transfer Catalysts (2012)
  • Author(s): E. Yamamoto et al
  • Journal Title: Org. Lett. Volume: 14 Issue: 24 Pages: 6178-6181
  • DOI: 10.1021/ol3027363
  • Peer Reviewed
• [Journal Article] Catalytic Asymmetric Hydrolysis : Asymmetric Hydrolytic Protonation of Enol Esters Catalyzed by Phase-Transfer Catalysts (2011)
  • Author(s): E.Yamamoto, et al
  • Journal Title: Chemistry A European Journal Volume: 17 Issue: 26 Pages: 7178-7182
  • DOI: 10.1002/chem.201100833
  • Peer Reviewed
• [Presentation] シンコナアルカロイド由来キラル相間移動触媒を用いた塩基加水分解による N 保護アミノ酸エステル類の動的速度論的光学分割 (2013)
  • Author(s): 中村亮太・山本英治・濱崎昭行・石田玉青・徳永信
  • Organizer: 日本化学会第93春季年会
  • Place of Presentation: 草津
  • Year and Date: 2013-03-23
• [Presentation] Asymmetric Base Hydrolysis of Esters Catalyzed by Chiral (Phase-transfer Catalysts Derived from Cinchona Alkaloids) (2012)
  • Author(s): Makoto Tokunaga
  • Organizer: First Japan-USA Organocatalytic Symposium
  • Place of Presentation: Hawaii, USA
  • Year and Date: 2012-12-17
• [Presentation] Asymmetric Hydrolytic Protonation of Alkenyl Esters and Hydrolysis of Axially Chiral (2012)
  • Author(s): Nagai A, Yamamoto E, Hamasaki A, Ishida T, Kamachi T, Yoshizawa K, Tokunaga M
  • Organizer: Compounds with Chiral Phase-Transfer Catalysts First Japan-USA Organocatalytic Symposium
  • Place of Presentation: Hawaii, USA
  • Year and Date: 2012-12-16
• [Presentation] Dynamic Kinetic Resolution of N-protected amino acid esters by base hydrolysis with Chiral Phase-Transfer Catalysts (2012)
  • Author(s): Nakamura R, Yamamoto E, Hamasaki A, Ishida T, Tokunaga M
  • Organizer: First Japan-USA Organocatalytic Symposium
  • Place of Presentation: Hawaii, USA
  • Year and Date: 2012-12-16
• [Presentation] Asymmetric Hydrolysis of Esters with Chiral Phase-transfer Catalysts (2012)
  • Author(s): Eiji Yamamoto, Ayano Nagai, Ryota Nakamura, Katsuma Takehisa, Akiyuki Hamasaki, Tamao Ishida, Takashi Kamachi, Kazunari Yoshizawa, and Makoto Tokunaga
  • Organizer: The 2 nd International Conference on MEXT Project of Integrated Research on Chemical Synthesis, "Molecular Functions in Complex Systems"
  • Place of Presentation: 名古屋
  • Year and Date: 2012-12-11
• [Presentation] シンコナアルカロイド由来四級アンモニウム塩を用いるエステルの触媒的不斉加水分解反応 (2012)
  • Author(s): 徳永信
  • Organizer: 第5回有機触媒シンポジウム
  • Place of Presentation: 東京
  • Year and Date: 2012-10-27
• [Presentation] Asymmetric Base Hydrolysis of Esters Catalyzed by Chiral Quaternary Ammonium Salts (Keynote) (2012)
  • Author(s): E. Yamamoto, D. Gokuden, A. Nagai, R. Nakamura, K. Takehisa, A. Hamasaki, T. Ishida, T. Kamachi, K. Yoshizawa, M. Tokunaga
  • Organizer: 17 th Malaysian Chemical Congress 2012 (17MCC)
  • Place of Presentation: Kuala Lumpur, Malaysia
  • Year and Date: 2012-10-17
• [Presentation] キラル相間移動触媒を用いたN-保護アミノ酸エステル類の不斉塩基加水分解反応 (2012)
  • Author(s): 中村亮太、山本英治、濱崎昭行、石田玉青、徳永信
  • Organizer: 有機合成化学協会九州山口支部 第24回若手研究者のためのセミナー
  • Place of Presentation: 福岡
  • Year and Date: 2012-08-25
• [Presentation] シンコナアルカロイド由来相間移動触媒を用いたアミノ酸エステル類の不斉加水分解反応 (2012)
  • Author(s): 中村亮太・山本英治・濱崎昭行・石田玉青・徳永信
  • Organizer: 第49回化学関連支部合同九州大会
  • Place of Presentation: 北九州
  • Year and Date: 2012-06-30
• [Presentation] シンコナアルカロイド由来相間移動触媒を用いたエノールエステル類の不斉加水分解反応 (2012)
  • Author(s): 永井あやの 山本英治 濱崎昭行 石田玉青 徳永信
  • Organizer: 第49回化学関連支部合同九州大会
  • Place of Presentation: 北九州
  • Year and Date: 2012-06-30
• [Presentation] キラル四級アンモニウム塩を触媒に用いる エステルの不斉加水分解反応 (2012)
  • Author(s): 徳永 信
  • Organizer: 新学術領域研究「有機分子触媒による未来型分子変換」第1回全体会議
  • Place of Presentation: 京都
  • Year and Date: 2012-06-09
• [Presentation] Phase-Transfer Catalytic Base-Hydrolysis of Esters (2012)
  • Author(s): E. Yamamoto, R. Nakamura, A. Nagai, T. Kamachi, K. Yoshizawa, A. Hamasaki, T. Ishida, M. Tokunaga
  • Organizer: Symposium on Molecular Chirality ASIA 2012 (MS ASIA 2012)
  • Place of Presentation: Fukuoka
  • Year and Date: 2012-05-17
• [Presentation] 不斉相間移動触媒を用いたジエニルエステル類およびβ-ジケトン類の加水分解的不斉プロトン化反応 (2012)
  • Author(s): 山本英治・御供田大地・永井あやの・蒲池高志・吉澤一成・濱崎昭行・石田玉青・徳永信
  • Organizer: 日本化学会第92 春季年会
  • Place of Presentation: 横浜
  • Year and Date: 2012-03-26
• [Presentation] キラル相間移動触媒によるエステル類の不 斉加水分解反応 (2012)
  • Author(s): 徳永 信
  • Organizer: 早稲田大学グローバルCOE「実践的化学知」第3回 キラルサイエンス&テクノロジー シンポジウム
  • Place of Presentation: 東京
  • Year and Date: 2012-02-14
• [Presentation] Hydrolytic Enantioselective Protonation Catalyzed by Chiral Quaternary Ammonium Salts (2011)
  • Author(s): E. Yamamoto, D. Gokuden, A. Nagai, R. Nakamura, A. Hamasaki, T. Ishida, M. Tokunaga
  • Organizer: The 4 th Pusan National Univ. Global COE Kyushu Univ. Joint Symposium on Molecular Science and Technology
  • Place of Presentation: Busan、Korea
  • Year and Date: 2011-12-21
• [Presentation] Alcoholysis and Hydrolysis of Alkenyl Esters and Ethers with Homogeneous Catalysis (2011)
  • Author(s): E. Yamamoto, H. Ito, A. Hamasaki, T. Ishida and M. Tokunaga
  • Organizer: The 6th International Conference on Cutting-Edge Organic Chemistry in Asia (ICCEOCA-6) and The 2nd New Phase International Conference on Cutting-EdgeOrganic Chemistry in Asia
  • Place of Presentation: 香港、china
  • Year and Date: 2011-12-14
• [Presentation] Asymmetric Hydrolysis of Esters Catalyzed by Phase Transfer Catalysts International (2011)
  • Author(s): E. Yamamoto, A. Nagai, R. Nakamura, A. Hamasaki, T. Ishida, M. Tokunaga
  • Organizer: Symposium on Catalysis and Fine Chemicals
  • Place of Presentation: Nara, Japan
  • Year and Date: 2011-12-05
• [Presentation] Asymmetric Hydrolytic Protonation of Dienyl Esters and Diketones for the Catalytic Enantioselective Synthesis of -Tertiary Chiral Cyclic Enones (2011)
  • Author(s): Eiji Yamamoto, Daichi Gokuden, Ayano Nagai, Akiyuki Hamasaki, Tamao Ishida, Makoto Tokunaga
  • Organizer: The 2011 Global COE International Symposium on Future Molecular Systems
  • Place of Presentation: Fukuoka Japan
  • Year and Date: 2011-11-25
• [Presentation] 相間移動触媒を用いたエステル類の不斉加水分解 (2011)
  • Author(s): 山本英治、中村亮太、永井あやの、大村直也、佐久間毅、濱崎昭行、徳永信
  • Organizer: 第48回化学関連支部合同九州大会
  • Place of Presentation: 北九州
  • Year and Date: 2011-07-09
• [Presentation] 相間移動触媒を用いたエステル類の不斉加水分解 (2011)
  • Author(s): 山本 英治・永井 あやの・濱崎 昭行・徳永 信
  • Organizer: 第21回福岡万有シンポジウム
  • Place of Presentation: 福岡
  • Year and Date: 2011-05-21
• [Presentation] 相間移動触媒を用いた塩基加水分解による軸不斉化合物の不斉加水分解 (2011)
  • Author(s): 永井 あやの・山本 英治・濱崎 昭行・徳永 信
  • Organizer: 日本化学会第91春季年会
  • Place of Presentation: 横浜
  • Year and Date: 2011-03-28
• [Presentation] 相間移動触媒を用いた塩基加水分解反応によるアズラクトン類の動的速度論分割 (2011)
  • Author(s): 中村 亮太・山本 英治・濱崎 昭行・徳永 信
  • Organizer: 日本化学会第91 春季年会
  • Place of Presentation: 横浜
  • Year and Date: 2011-03-27
• [Presentation] 相間移動触媒を用いたエノールエステル類の不斉加水分解 (2011)
  • Author(s): 山本 英治・永井 あやの・濱崎 昭行・徳永 信
  • Organizer: 日本化学会第91 春季年会
  • Place of Presentation: 横浜
  • Year and Date: 2011-03-26
• [Presentation] キラル相間移動触媒を用いたエステル類の不斉加水分解 (2011)
  • Author(s): 山本 英治, 永井 あやの, 中村 亮太,濱崎昭行, 石田 玉青, 徳永 信
  • Organizer: 第100回有機合成シンポジウム
  • Place of Presentation: 東京
• [Presentation] Asymmetric Base Hydrolysis of Esters Catalyzed by Chiral Quaternary Ammonium Salts
  • Author(s): M. Tokunaga
  • Organizer: 17 th Malaysian Chemical Congress 2012 (17MCC),
  • Place of Presentation: マレーシア
  • Invited
• [Presentation] キラル相間移動触媒によるエステル類の不斉加水分解反応
  • Author(s): 徳永 信
  • Organizer: 早稲田大学グローバルCOE「実践的化学知」第3回 キラルサイエンス＆テクノロジー シンポジウム(招待講演)
  • Place of Presentation: 早稲田大学、東京
• [Book] Carreira E.M. and Yamamoto H. (eds.) Comprehensive Chirality, Volume 5 (Asymmetric Oxidation Reduction, C-N) (2012)
  • Author(s): Tokunaga, M.; Hamasaki, A
  • Publisher: Amsterdam: Elsevier
• [Patent(Industrial Property Rights)] エステルの不斉加水分解方法 (2011)
  • Inventor(s): 徳永 信、濱崎昭行、山本英治、佐久間毅、大村直也、永井あやの、中村亮太
  • Industrial Property Rights Holder: 九州大学
  • Industrial Property Number: 2011-006529
  • Filing Date: 2011-01-16