The Study on Asymmetric Addition Reaction Catalyzed by Camphorsulfonamide-derived-amine and Pyrrolidine–camphorsulfonamide Derivatives

• Main Authors: Huang, Yu-Chao, 黃昱超
• Other Authors: Uang, Biing-Jiun
• Format: Others
• Language: zh-TW
• Published: 2014
• Online Access: http://ndltd.ncl.edu.tw/handle/rm8sw7

博士 === 國立清華大學 === 化學系 === 102 === This thesis deals with the application of camphor-derived organocatalyst in asymmetric addition reaction. The fisrt part discusses the asymmetric aldol reaction of 2,2-dimethyl-1,3-dioxan-5-one with aldehydes in the presence of 10 mol% organocatalyst 42 and 20 mol% p-nitrobenzoic acid to give aldol products in good yields with high enatio- and diastereoselectivities. (up to 99% ee, 4:96 dr) The second part deals with the development of camphorsulfonamdie-derived (2S,4R)-4-hydroxy-L-prolinamide 54b as organocatalyst. Catalyst 54b is able to catalyze asymmetric Michael addition of 2,2-dimethyl-1,3-dioxan-5-one to nitro alkenes. The asymmetric reaction could give γ-nitro-dihydroxyacetones in good yields with high enatio- and diastereoselectivities (up to 94% ee, 91:9 dr) in the presence of 10 mol% organocatalyst 54b, 5 mol% 2,4-dinitrophenol and 5 equiv. of water in toluene. The third part discusses pyrrolidine-camphorsulfonamide based catalyst 30 in the asymmetric catalytic Michael addition reaction of nitroalkanes to alpha,beta-unsaturated aldehydes without the addition of acid additive to produce desired products with up to 99% ee and good yields. The main advantage of this catalyst is high efficiency and enantioselectivity with low catalytic loading (1-2 mol%). These remarkable advantages make this approach very suitable for gram-scale synthetic use.