Studies On Atom Transfer Radical Addition Of Several Kinds Of Small Organic Molecules To Alkynes

The selective activation of(sp~3)C-H bond promoted by free radicals to construct carbon-carbon bond represents one of the most green and efficient synthesis strategies.In this paper,several methods for the construction of C-C bonds by selective radical addition of small organic molecules such as alcohols,ketones,esters,nitriles to aliphatic alkynes have been developed.Firstly,the latest research progresses of free radical promoted C-C bond construction was summarized.Secondly,several methods via selective radical functionalization of(sp~3)C-H bond were introduced in details,and then C-C bond was constructed by addition reaction with alkyne.Finally,the research field is summarized and prospected.This thesis mainly contains the following five sections:Chapter 1 summarizes the latest research progresses of free radical-promoted carbon-carbon bond construction in recent years.This chapter is divided into two parts.In the first part,the reaction of alkynes is discussed.In the second part,the progresses of(sp~3)C-H selective activation of alcohols,ketones,esters and nitriles to construct C-C bonds were introduced in details.In Chapter 2,the atom-transfer radical addition reaction of simple alcohols to unactivated alkynes was demostrated.A series of allyl alcohols with trans-configuration were synthesized with tert-butyl peroxide as free radical initiator,potassium fluoride as additive and alcohol as solvent.Chapter 3 described the radical reaction of unactivated alkynes with ketones and esters.A series ofβ-γunsaturated carbonyl compounds with trans-configuration were synthesized with tert-butyl peroxide as free radical initiator and ketone or ester as solvent.Chapter 4 introduced the atom-transfer radical addition reaction of acetonitrile to unactivated alkynes.A wide range of E-β,γunsaturated nitriles could be isolated via this method.At the end of this thesis,the atom-transfer radical addition reaction of several categories of small organic molecules to alkynes via selective functionalization the(sp~3)C-H bond developed by our research group was summarized,and the future studies in this field is prospected.