Radical Difunctionalization Of Alkenes Via Esterification

Alkenes as the cornerstone of chemical materials are also readily available natural products.Many reactions of simple alkenes have been used in industrial production,Representative reactions include oxidation of olefins,hydrofunctionalization,hydrogen reduction,and polymerization of olefins.In recent years,the difunctionalization of simple alkenes has developed into a very useful method to synthesis the molecular skeleton of complex structures,which has attracted the attention of chemists to develop new functionalization strategies.In particular,the intermolecular difunctionalization of simple alkenes can add two functional groups to molecular in one step.The 1,2-difunctionalization of alkenes is an effective method for increasing molecular diversity.In this thesis,Copper-catalyzed oxidative intermolecular 1,2-alkylesterification of styrenes with ethers and acids is disclosed.A simple protocol for the three components 1,2-bromoesterification of alkenes with acids and N-bromosuccinimide under electrochemical oxidative conditions is described.This paper mainly includes the following contents:(1)The first chapter,the progress of recent oxidative difunctionalization of alkens are described in detail.Mainly:(i)Recent advances in transition-metal-catalyzd difunctionalization of alkenes using Cu or Fe;(ii)Recent advances in transition-metal-catalyzd difunctionalization of alkenes using Co,Fe,Ni,Pd and Ag;(iii)Recent advances in Electrochemical difunctionalization of alkenes.(2)In the second chapter,di-tert-butyl peroxide(DTBP)initiate the1,2-alkylesterification of alkenes reaction with acid and tetrahydrofuran was studied in detail.Ether compounds such as diethyl ether,tetrahydrofuran and 1,4-dioxane are simple and readily available chemical andindustrial materials and are also an important class of solvents.This method utilizes DTBP as an oxidant to efficiently construct C–O and C–C bonds in one step through probableradical and electrophilic alkylation processes,respectively,and avariety of functional groups are well tolerated.Furthermore,the possible mechanism of the copper-catalyzed 1,2-alkylesterification of alkenes is proposed.The result shows that copper-catalyzed oxidative the epoxy ether to generate alkyl radical under heating,the alkyl radical was added alkenes and coupled with nucleophile via a single electron transfer(SET)to produce an1,2-alkylesterification product.(3)In the third chapter,the bromoesterification of alkenes reaction using carbon rod as anode and cathode was studied in detail.The reaction achieves1,2-bromoesterification of alkenes with N-bromosuccinimide(NBS)and carboxylic acids,and the reaction conditions are mild.In this transformation,a variety of alkenes including styrenes and cycloolefines were well tolerated and reacted with aro-matic acids,aliphatic acids and amino acids for the construction of bromines derivatives via oxidative C-Br/C-O difunc-tionalization.A scientific mechanism is proposed after studying the cyclic voltammetry curve.The result shows that TEMPO loses electrons at the anode to generate TEMPO~+,and N-bromosuccinimide(NBS)and alkenes was oxidized by TEMPO~+to generate cyclic bromonium ion intermediat.The cyclic bromonium ion intermediate coupled nucleophile,which is acids,to give the1,2-bromoesterified product.