Cinchona-Based Primary Amine Catalyzed Asymmetric Michael Reactions

Chiral primary amine catalysts play an important role in the field of asymmetric synthesis. Cinchona derivatives greatly expanded the application of the primary amines, which can catalyze some reactions those may not be functionalized by secondary amines. Recent advances in the asymmetric reactions catalyzed by the cinchona-based primary amines were summarized and reviewed. On this basis, the properties of the cinchona-based primary amines and the supported ones in Michael reactions were invested deeply. This dissertation includes the following three parts:(1) Recent advances in the asymmetric reactions catalyzed by cinchona-based primary amines were summarized and reviewed.(2) Various substituted nitrodienes were synthetized in high yields. An organocatalytic Michael reaction of cycloheptanone and cyclooctanone with nitrodienes catalyzed by a hydroquinine-based primary amine catalyst combined with a co-catalyst benzoic acid has been accomplished. The corresponding adducts were afforded in good yields (up to 88%) with good to excellent diastereoselectivities (up to 99:1 dr) and enantioselectivities (up to 99% ee). The absolute configurations of the Michael adducts were determined by comparing the electronic circular dichroism (ECD) spectra of the chiral product with calculated time-dependent density functional theory (TDDFT) results.(3) The asymmetric Michael reaction of 1,3-cyclic dicarbonyl compounds to α,β-unsaturated ketone catalyzed by quinine-based primary amine catalyst supported on thiolated pegs with different molecular weight was explored. When catalyst monomer was supported on PEG5000-SH, the corresponding adducts were given in the same enantioselectivities (80% ee) as catalyzed by catalyst monomer.