Multifunctionalization Of Unactivated Cyclic Ketones Via Synergistic Catalysis Of Copper And Diarylamine:Access To Cyclic ?-Enaminone

The catalysis of organic reactions by transition metals(transition metal catalysis)has been established as one of the most useful and powerful tools in organic synthesis.Meanwhile,over the past decade,organocatalysis,in which small organic molecules(organocatalysts)act as catalytically active species,has grown explosively to become one of the most exciting research areas in current organic chemistry.One of the main advantages of organocatalysis is that organocatalysts can promote various organic transformations through unique activation modes as compared to transition metal catalysis.In recent years,the concept of combining transition metal catalysis and organocatalysis has emerged as a promising strategy for developing new and valuable reactions,and has attracted considerable attention as it could potentially enable unprecedented transformations not currently possible by use of the transition metal complex or the organocatalyst alone.Despite the application of synergistic catalysis in ?-or ?-functionalization of unactivated cyclic ketones has recently made great progress,the multi-functionalization version has not been achieved.Herein,we wish to report the first case to realize multi-functionalization of unactivated cyclic ketones via synergistic catalysis of copper and diarylamine for the synthesis of cyclic ?-enaminone.O-benzoylhydroxylamines are the most widely used electrophilic aminating reagents,which are easily prepared,fairly stable,and also present excellent reactivity in transition-metal-catalyzed C-N bond formation.So it has been widely studied in recent years?This methodology utilizes O-benzoylhydroxylamines as both amination reagents and oxidants,and is featured with its mild conditions,broad substrate scope and excellent selectivity profile?...