RHODIUM/PALLADIUM-CATALYZED ENANTIOSELECTIVE ADDITION REACTIONS

Abstract

Transition metal-catalyzed carbon-carbon bonds formations are of great importance in organic synthesis. Especially, the rhodium/palladium-catalyzed asymmetric addition reactions have attracted great attentions because of their high efficiency, special selectivity and mild reaction conditions. In this thesis, newly designed C1 symmetric chiral dienes were employed to rhodium-catalyzed asymmetric 1,4-addition of organoboron reagents to enones. These simple synthesis C1 symmetric chiral dienes demonstrated higher catalytic activities and enantioselectivities in a wide substrate scope, compared with standard chiral dienes. In addition, amino acid derived phosphinooxazoline and phosphine-imine ligands were applied to the palladium-catalyzed asymmetric arylation reactions. The cationic palladium/phosphinooxazoline catalyst presented very high enantioselectivities in arylation of fluoroalkyl substituted 2-quinazolinone derivatives. Besides, the phosphine-imine ligands were for the first time applied to the palladium-catalyzed asymmetric arylation reactions, in which high catalytic activities, useful level of enantioselectivies, and wide scope were obtained.