Study On Inexpensives Metals-Catalyzed Radicals Difunctionalization Reaction Of Alkenes And Alkynes

Alkenes and alkynes as important chemical raw materials and organic synthesis raw materials,play a very important role in the development of organic synthesis because of their low cost,easy availability and high reactivity.The difunctionalization reaction of alkenes and alkynes can be used to synthesize multi-site reaction products in one step,and convert starting materials with simple structures into complex compounds with biological or pharmaceutical activities.Therefore,it has received extensive attention from scientists.Among them,by the way of inexpensive metal-catalyzed radicals difunctionalization reaction of alkenes and alkynes have been realized,and a series of outstanding research results have been achieved.However,how to regulate the reactivity of radicals and realize the chemistry and regioselective difunctionalization reaction of alkenes and alkynes is still an urgent problem to be solved.Therefore,the development of the new catalytic controllable system to realize the efficient and selective difunctionalization reaction of olefins and alkynes is of great significance to the development of organic chemistry.This thesis mainly focuses on the radical difunctionalization reaction regulated by inexpensive metals.Achieved herein include dual photoredox and nickel catalyzed radical 1,2-addition reaction of aryl bromides to alkynes,and iron-catalyzed solvent-tuned chemoselective carboazidation and diazidation reaction of alkenes.The thesis content includes the following two parts:Part I:We used aryl bromide as the bromine and aryl group sources through visible-light photoredox and nickel metals synergistic catalysis strategy.Alkynes Selective 1,2-addition aryl bromides to alkynes was realized.The reaction used visible-light to promote the generation of bromine radical from nickel metallic species,and converts a wide range of（hetero）aryl bromides and terminal alkynes into regioselective alkenyl bromide products under redox neutral conditions.This method can also be extended to other substrates,such as intramolecular alkynes,1,6-diene,1,6-diyne and1,6-enyne.The mild reaction conditions and good substrate applicability provide a new idea for the realization of atom economy and regioselective difunctionalization of alkynes.Part II:We used dichloromethane as the precursor of carbon radicals,TMSN₃ as the precursor of azide radicals and peroxide as the oxidant,the iron-catalyzed chloromethyl azide reaction of alkenes was realized.Using simple solvent control,the olefin diazide reaction can be realized under the same catalytic system.This reaction has good functional group compatibility and substrate suitability,and a series of activated and non-activated alkenes underwent this transformation smoothly,yielding the desired products with high efficiency.