Iron-catalyzed De-aromatization Amination Reaction Efficiently Constructs CN Bonds And Palladium-catalyzed Asymmetric Alkylation Reactions

Transition metal catalysis to construct new chemical bonds has been widely applied in chemical synthesis,medicine and pesticide fields.Thus,it is one of the most forefront areas in recent decades.Transition metal catalysis has been widely applied to construct variety of chemical bonds.But,it is an important direction to construct different types chemical bonds according to the different sensitivity of substrate sites by transition metals.These include the metal-participated in the direct construction of C-C and C-N.And the combined catalytic of metals and chiral ligands.with the chiral inducted of the catalyst to construct the chiral quaternary carbon center.Therefore,taking full advantage of the special properties of transition metals,to build new chemical bonds still has important theoretical and practical significance.The content of this paper consists of the following two parts:?1?Fe-catalyzed dearomative amination of?-naphthols with aryl azides was studied.The method constructs a nitrogen-containing quaternary carbon center catalyzed by cheap and readily available iron salt FeCl₂,and affords a series of?-amino-?-naphthalenones in good to excellent yields under simple and mild reaction conditions.Experimental and computational studies suggest that the reaction is initiated by iron-iminyl diradical and followed by intramolecular hydrogen transfer to generate iron-aminyl radical and finally an intramolecular radical combination reaction.?2?Based on previous work,we synthesized a new type of chiral N,N,P ligands,and successfully applied such chiral catalysts in palladium catalyzed asymmetric allylic alkylation reactions to obtain chiral products with high enantioselectivities?up to 96%?and high yields?up to 99%?.Analysis experiment datas,it indicates that the chiral catalyst by the chiral ligand combined with palladium has a better chiral space,and can induce direction-attacked of reagents from one path to substrates,with an excellent yield and enantioselectivities of products.