Sustainable Amination Reactions Based On Rh(?)-Catalyzed Nitrene Transfer

Nitrogen compounds are prevalent structural motifs in natural products and bioactive pharmacetics with important applications in biomedicine,materials,agriculture and other s fields.Among many approaches toward nitrogen compounds,transition metal-catalyzed nitrene transfer reactions have emerged as a powerful and straightforward strategy.By using suitable nitrogen precursors and oxidants with metal catalysts,the in situ generated metal nitrene can aminate different kinds of substrates,such as hydrocarbons,olefins,and thioethers.However,these reactions heavily rely on toxic and volatile organic solvents,and selectivity and efficie nc y need further improvement for some inert substrates.In the light of sustainable organic synthes is,this dissertation focused on developing more benign protocols to construct aliphatic amines via Rh(?)-catalyzed nitrene transfer.The main contents include the following sections:First,we have realized Rh(?)-catalyzed intermolecular C(sp³)–H amination performed in aqueous phase,which proves good compatablity of nitrene intermediate with water.This protocol features benign conditions,broad substrate scope including benzylic,secondary and tertiary C(sp³)–H bonds,and is applicable for late-stage amination of amino acid derivatives and ibuprofen methyl ester.Moreover,we have developed Rh(?)-catalyzed cascade al yl sulfides amination/[2,3]-sigmatropic rearrangement reaction with in situ generated aminoiodinane in water.This reaction features the high chemoselectivity and excel ent tolerance of different functio na l groups,provides a novel green method to build al ylic amine motifs.Furthermore,we described the first mechanochemical Rh(?)-catalyzed C(sp³)–H amination.This state-of-the-art technology necessitates much enonomized loading of Rh₂(esp)₂,significantly shortened reaction time in comparison to solution-based catalytic system.It can selectively aminate not only various unactivated alkanes but also complex natural products and drug molecules in high efficiency.