Palladium-Catalyzed Intramolecular Difunctionalizations Of Unactivated Alkenes

This thesis focuses on the palladium-catalyzed intramolecular difunctionalization of unactivated alkenes.By using high-valent palladium strategy,a palladium-catalyzed intramolecular regioselectivity diamination of alkenes was developed via a Pd（II）/Pd（IV）catalytic cycle.And a palladium-catalyzed intramolecular aminotrifluoromethylthiolation of alkenes was also realized.The main contents are listed as following.1.Ligand-controlled 6-endo and 5-exo diamination of unactivated alkenesBased on the ligand modification,a palladium-catalyzed regioselective diamination of alkenes was developed.This reaction employed N-fluorobenzenesulfonimide（NFSI）as both oxidant and amine source,and palladium acetate as the optimal catalyst.The 6-endo diamination occurred predominantly to afford the 3-amino piperidines with less steric hindered quinox ligand,and 5-exo diamination occurred to provide amino pyrrolidines with sterically bulky pyox.2.Palladium-catalyzed intramolecular 5-exo aminotrifluoromethylthiolation of alkenesA palladium-catalyzed aminotrifluoromethylthiolation reaction of homoallyl amines was surveyed,which achieved the efficient formation of both C-N and C-S bonds.This reaction employed palladium acetate as the optimal catalyst,Ag SCF₃ as the SCF₃ source and selectfluor as the oxidant,providing the 5-exo aminotrifluoromethylthiolation products as major products.A series of trifluoromethylthiolated pyrrolidines were obtained in moderated yields under mild condition,which afforded a new access to trifluoromethylthiolated nitrogen containing heterocycles.