Asymmetric Base Hydrolysis of Esters using Zwitterionic Nucleophilic Catalyst

2017 Fiscal Year Final Research Report

• Project/Area Number: 16H07042
• Research Category: Grant-in-Aid for Research Activity Start-up
• Allocation Type: Single-year Grants
• Research Field: Synthetic chemistry
• Research Institution: Kyushu University
• Principal Investigator: Yamamoto Eiji 九州大学, 理学研究院, 助教 (70782944)
• Research Collaborator: TOKUNAGA Makoto (40301767) ; MURAYAMA Haruno (90426528) ; YOSHIZAWA Kazunari (30273486) ; KAMACHI Takashi (40403951)
• Project Period (FY): 2016-08-26 – 2018-03-31
• Keywords: エステル加水分解 / 相間移動触媒 / アンモニウム塩 / 動的速度論的光学分割 / 光学活性アミノ酸 / 不斉プロトン化 / 光学活性ケトン

Outline of Final Research Achievements

Optically active carboxylic acids are an important synthetic intermediate for pharmaceuticals. Hydrolase-catalyzed asymmetric ester hydrolysis is an important method to access the compounds. However, the methods still have several drawbacks such as low specific activity of the enzymes. Notwithstanding the recent advances in asymmetric catalysis, stereocontrol in ester hydrolysis with synthetic catalysts has also remained a formidable challenge.
In this study, we successfully developed phase-transfer catalytic base hydrolysis of N-protected aminoacid esters, which proceeds via dynamic kinetic resolution to provide the corresponding products in moderate to good yields (up to 99%) with up to 96:4 er. In addition, we also succeeded in developing a hydrolytic enantioselective protonation of alkenyl esters with a novel catalyst.

Free Research Field

有機合成