Iodine-mediated Rearrangement Of Tertiary Alkyl Amines

Rearrangement reactions have drawn considerable attentions from chemists because of their high atomic economy.Among them,the 1,2-C to N migration is widely used in the synthesis of natural products and drug molecules.To date,various such reactions have been reported;however,most of current 1,2-C to N migration reactions use amides,azides,N-haloamines,hydroxylamines and their derivatives as substrates.Only a few studies have been done to investigate rearrangement reactions of amines.In this dissertation,the readily available tertiary alkyl amines are directly used as substrates for the iodine-mediated oxidative rearrangement reactions.Iodine can effectively promote the 1,2-aryl migration(C to N)of these compounds under basic conditions.The optimization of reaction conditions demonstrated that cesium carbonate is the optimal base.The resulting rearrangement imine products can be directly reduced to afford the corresponding aromatic secondary amines.In addition,these imine intermediates can be transformed to other aromatic secondary amines by the reactions with different nucleophiles.The present rearrangement reaction requires no pre-functionalization of the amino group in the substrates and no use of transition metal catalysts.It is operationally simple with wide substrate scope,and can be conducted in a gram scale.