8-Aminoquinoline-directed Nickel-catalyzed Selective Bifunctionalization Of Alkenes

The simultaneous introduction of two different functional groups to olefins by a one-step reaction using industrially simple and readily available olefins as raw materials is an efficient and rapid method for the construction of complex molecules.In recent years,the reaction of nickel-catalyzed difunctionalization of olefins has received much attention because of its ability to achieve high regioselectivity and stereoselectivity of molecules.The more demanding conditions of the conventional synthesis methods lead to limitations of substrates,limitations of ligands,and poor regioselectivity,all of which are drawbacks that cannot be ignored.Achieving selective difunctionalization of olefins has been the focus of research workersThe main research work in this paper is based on the study of selective difunctionalization reactions of unactivated olefins catalyzed by transition metal nickel.In the first part of the work,this chapter used 3-butenoic acid as a substrate to react with arylboronic acids and organohalides to obtain 2,1-region selective diarylation and arylalkylation products.In the second part of the work,the strategy was extended to longer carbon chain lengths and olefins further away from the functional group for remote aryl alkylation reactions to obtain remote aryl alkylation products with excellent diastereoselectivity.And the mechanism of remote aryl alkylation of olefins was verified by controlled experiments,radical clock experiments,reaction kinetics experiments and density flooding theory（DFT）calculations as a Ni^Ⅰ-Ni^Ⅲ-Ni^Ⅰ reaction mechanism.These methods can also be applied to the late modification of complex molecules in pharmacology.Finally,this paper explores the base catalyzed hydrosulfuration reactions of olefins by a guided strategy and yields excellent regioselective products.The establishment of these synthetic methodologies provides novel synthetic pathways for the formation of new C-C and C-S bonds,as well as more possibilities for other functionalization reactions of unactivated olefins with longer carbon chains catalyzed by transition metals through a guided strategy,as well as a foundation for the continued development of guided strategy olefin hydrosulfation reactions.