銀触媒を用いる脂肪族アルデヒドの三成分連結型不斉 mnnich 反.pdfVIP

銀触媒を用いる脂肪族アルデヒドの三成分連結型不斉Mannich 反応および Aza-Dields-Alder 反応の開発 Three-Component Ag-Catalyzed Enantioselective Vinylogous Mannich and Aza-Diels-Alder Reactions with Alkyl-Substituted Aldehydes 岡山大学大学院自然科学研究科機能分子化学専攻 萬代 大樹 Division of Chemistry and Biochemistry, Graduate School of Natural Science and Technology, Hiroki Mandai 派遣期間 ２００６年４月３日～２００８年９月１３日 April 3, 2006~September 13, 2008 研究機関 Boston College 研究指導者 Professor Amir H. Hoveyda 英文サマリー Efficient protocols for three-component catalytic enantioselective vinylogous Mannich (VM) reactions of alkyl-substituted aldimines (including those bearing heteroatom-containing substituents) and readily available siloxyfurans are presented. High efficiency and stereoselectivity is achieved through the use of o-thiomethyl-p -methoxyaniline-derived aldimines. Reactions, performed under an atmosphere of air and in undistilled THF, can be promoted in the presence of as little as 1 mol % of easily accessible amino acid-based chiral ligands and commercially available AgOAc. The desired products are obtained in 44 to 92% yield, and in up to 98:2 diastereomer and 99: 1 enantiomer ratio (98% ee). Removal of the N-activating group is performed through a one-vessel oxidation/hydrolysis operation, which proceeds via a stable aza-quinone (characterized by X-ray crystallography). Additionally, Ag-catalyzed aza-Diels-Alder reactions of the alkyl-substituted aldimines bearing the structurally modified N-aryl unit afford enantiomerically enriched (up to 95% ee) products in up to 88% yield. 1. Introduction マンニッヒ反応は，有機合成化学において重要な炭素-炭素結合生成反応の一つであり， この反応によって得られるβ-アミノカルボニル化合物は，光学活性含窒素化合物や生理 活性をもつ天然化合物を合成する上で重要