Diastereo- and Enantioselective Reaction of Carbocation

Research Project

Project/Area Number	24590030
Research Category	Grant-in-Aid for Scientific Research (C)
Allocation Type	Multi-year Fund
Section	一般
Research Field	Chemical pharmacy
Research Institution	Meiji Pharmaceutical University
Principal Investigator	NOJI MASAHIRO 明治薬科大学, 薬学部, 講師 (80312073)
Project Period (FY)	2012-04-01 – 2015-03-31
Project Status	Completed (Fiscal Year 2014)
Budget Amount *help	¥5,330,000 (Direct Cost: ¥4,100,000、Indirect Cost: ¥1,230,000) Fiscal Year 2014: ¥1,690,000 (Direct Cost: ¥1,300,000、Indirect Cost: ¥390,000) Fiscal Year 2013: ¥1,820,000 (Direct Cost: ¥1,400,000、Indirect Cost: ¥420,000) Fiscal Year 2012: ¥1,820,000 (Direct Cost: ¥1,400,000、Indirect Cost: ¥420,000)
Keywords	希土類ルイス酸 / ジカルボニル化合物 / 錯体構造 / ジアステレオ選択性 / エナンチオ選択性 / カルボカチオン / キラルイオンペア / 希土類錯体 / チオウレア誘導体 / ビナフチルクラウン化合物 / 光学活性チオウレア / キノリン誘導体 / 希土類トリフラート / 紫外可視吸収スペクトル
Outline of Final Research Achievements	UV-Vis absorption spectrum and ESI-MS analysis revealed that diastereoselectivity of the rare earth metal triflate-catalyzed secondary benzylation of ketoester was controlled by the steric effect of 1:1:1 complex of the ketoester enol form, the ketoester keto form, and the lutetium ion. Optically active rare earth metal Lewis acids and chiral thiourea catalysts were examined for the enantioselective reaction of the cationic species. Chiral thiourea-catalyzed reaction of the allylic alcohol and the sulfonamide gave quinoline derivative enantioselectively via a kinetic resolution of the quinoline product.