Iron-catalyzed Remote Functionalization Via Selective Cleavage Of Inert C(sp~3)-H Bond Of Alkenes Enabled By 1,n-Hydrogen-Atom-Transfer

Carbon and hydrogen are the most abundant elements in organic molecules.As one of the most step-economic and atom-economic method,selective C-H functionalization has been greatly developed over the years.Compared with traditional TM-catalyzed C-H activation/functionalization where two-electron chemistry empowers the whole process,radical/one-electron strategy stands out as better alternative when it comes to the functionalization selectively with general substrate scope.However,most of these reactions relied on highly instable radical initiator such as Nitrogen radical or Oxgen radical;the more stable yet easily accessed Carbon radical has been less studied.Very recently,some impressive progress have been made in Carbon radical-initiated C-H functionalization,while they were mostly confined to the functionalization on relatively activated C-H bond,functionalization on the inert,alkyl C(sp3)-H bond still,remain challenging.Concerning these challenges yet great opportuinities,we,for the first time,propose the iron-catalyzed remote functionalization on inert C(sp3)-H bond.Chapter 1:Research backgroundWe comprehensively described the development of C-H functionalization with radical-intiated reactions previously.They were mainly constituted of Nitrogen,Oxygen and Carbon radical-intiated reactions.Moreover,we have also reasoned several key components in order to realize effective remote C-H functionalization including configuration of transition state,BDE(Bond Diassociation Enengy)difference,etc.Chapter 2:Iron-catalyzed remote azidotrifluoromethylation of inert alkenes.We developed the first iron-catalyzed,remote functionalization of inert C(sp3)-H.It has excellent regioselective control,general substrate scope and mild condition.Furthermore,mechanistic studies confirmed a direct H-tranfer in 1,6-HAT process.Chapter 3:Iron-catalyzed remote diazidation of inert alkenes.Inspired by our previous progress,we take our carbon-radical-initiated remote functionalization one step further and realize the first remote diazidation of inert alkenes.The study clearly indicate our strategy's viability and advantage in re mote C(sp3)-H functionalization.