The Study Of Carbonylation Reactions Of Sulfonyl Chlorides/nitro Compounds

Since the first palladium-catalyzed carbonylation reaction was reported in 1974,carbonylation reaction has been rapidly developed in laboratory trial as well as in industrial production.Nowadays,carbonylation reactions have become a very important synthetic tool for the synthesis of a large number of useful chemicals that are important in our daily lives.For example,the industrial production of acetic acid by Monsanto process has become one of the main processes for the preparation of acetic acid in the world.Carbonylation reaction is an efficient way to synthesize aldehydes,carbonxylic acids,esters,ketones and amides,undoubtedly,which have widely applications in pesticides,pharmaceuticals and organic polymers.In this thesis,a series of transition-metal-catalyzed carbonylation reactions with sulfonyl chlorides/nitro compounds have been investigated:A palladium-catalyzed thiocarbonylation of aryl iodides with sulfonyl chlorides for the synthesis of thioesters was developed.Sulfonyl chlorides exhibited unique advantage as sulfur source without odor and catalyst poison properties,and both aryl and alkyl sulfonyl chlorides were tolerated well in this thiocarbonylative transformation.Meanwhile,Mo（CO）₆was used as both CO surrogate and reductive reagent makes this protocol much more attractive.A wide range of thioester products were obtained in moderate to excellent yields with good substrates compatibility.And apart from thioester,thioether can also be prepared.A nickel-catalyzed thiocarbonylation reaction of arylboronic acids with sulfonyl chlorides for the synthesis of thioesters was developed.Compare to traditional expensive palladium catalyst,nickel was used as a cheap catalyst in this aminocarbonylation reaction.By applying sulfonyl chlorides as an odourless,and low-toxicity sulphur source,both aryl and alkyl sulfonyl chlorides were suitable substrates in this procedure.With Mo（CO）₆as the solid CO precursor and reductant,a variety of thioesters were obtained in moderate to high yields.It was noteworthy that sulfonyl chlorides exhibited a unique advantage as an odorless sulfur source,which makes this approach much more attractive.A rhodium-catalyzed aminocarbonylation reaction of dimethyl carbonate with nitro compounds for the synthesis of acetamides was developed.In this aminocarbonylation reaction,dimethyl carbonate acted as a methylation reagent and a reaction medium,whereas Na I served as a cocatalyst to promote the conversion of dimethyl carbonate to CH₃I.With W（CO）₆as the CO source and reductant,a wide range of nitro compounds could be efficiently transferred to the corresponding acetamide derivatives in very good yields.Moreover,Phenacetin synthesis and last-stage modification of natural products were achieved via this aminocarbonylation strategy.This work provides a new synthetic pathway for the preparation of acetamides and highlights the application of dimethyl carbonate as both an active reagent and solvent in carbonyl-containing compound construction.