Asymmetric C-H oxidation with a designed self-assembling catalyst

Research Project

Project/Area Number	26670006
Research Category	Grant-in-Aid for Challenging Exploratory Research
Allocation Type	Multi-year Fund
Research Field	Chemical pharmacy
Research Institution	University of Shizuoka
Principal Investigator	Hamashima Yoshitaka 静岡県立大学, 薬学部, 教授 (40333900)
Project Period (FY)	2014-04-01 – 2016-03-31
Project Status	Completed (Fiscal Year 2015)
Budget Amount *help	¥3,770,000 (Direct Cost: ¥2,900,000、Indirect Cost: ¥870,000) Fiscal Year 2015: ¥1,300,000 (Direct Cost: ¥1,000,000、Indirect Cost: ¥300,000) Fiscal Year 2014: ¥2,470,000 (Direct Cost: ¥1,900,000、Indirect Cost: ¥570,000)
Keywords	酸化 / 不斉合成 / イオン対 / マンガン / ラクトン / 位置選択性 / 鉄 / 過酸化水素 / C-H結合
Outline of Final Research Achievements	In this project, we planned to use a concept of chiral ion-pairing to construct unique chiral environment around an oxidation catalyst toward the development of selective C-H oxidation transformations. First, iron or manganese-N5 complexes having chiral counter anions such as chiral phosphates and sulfonates were synthesized. Probably due to slow exchange rate of the counter anion, oxidation was retarded considerably. In contrast, CH oxidation proceeded in using a N4 ligand. When alkane with a carboxylic acid as a directing group was employed, the oxidation occurred at the benzylic position in good yield, affording the corresponding lactones with moderate enantioselectivity.