Transition Metal-catalyzed Alkoxycarbonylation And Trifluoromethylation Of Alkyl Iodides

This dissertation elaborates the alkoxycarbonylation and trifluoromethylation of alkyl iodides via copper-or cobalt-catalyzed/In-mediated and Cu-catalyzed/Ni-promoted conidtions,respectively.Detailed description is outlined as follows:In the first scetion,two protocols for the carbonylation of unactivated alkyl iododes with 1 atm CO are presented.Using Co?acac?₂ as the catalyst,zinc dust as the reductant,In Cl₃ as the additive and Mg CO₃ as the base,secondary alkyl iodides bearing a variety of functional groups are convereted to the alkyl esters in high efficiency in the presence of alcohol and 1 atm CO.Alternately,this section emphasizes the synthesis of alkyl esters via Cu-catalyzed and In-mediated alkoxycarbonylation of alkyl iodides in the presence of indium or In I.The reactions were suitable for primary,secondary and even tertiary alkyl esters,which represents an exceptionally rare example for the creation of quaternary carbon centers upon formation of esters.The preliminary mechanistic studies indicated that alkyl radicals were involved,and Cu/In/CO play a cooperative role in the carbonylation event.The second section of this thesis illustrates a reductive cross-electrophile coupling protocol for trifluoromethylation of alkyl iodides and Togni's reagent under Cu-catalyzed/Ni-promoted reaction conditions.The use of diboron esters as the terminal reductant allows the effective generation of the alkyl–CF₃ products with excellent functional group tolerance and broad substrate scope.A mechanism involving a reaction of alkyl–Cu ^I with Togni's reagent was proposed.