Conversion of a AuI Fluorido Complex into an N‐Fluoroamido Derivative: N−F versus Au−N Reactivity

Abstract

The AuI complex [Au{N(F)SO2Ph}(SPhos)] (SPhos=dicyclohexyl(2′,6′-dimethoxy[1,1′-biphenyl]-2-yl)phosphane) (2) bearing a fluoroamido ligand has been synthesized by reaction of the fluorido complex [Au(F)(SPhos)] (1) with NFSI (NFSI=N-fluorobenzenesulfonimide). A reaction with CO resulted in an unprecedented insertion into the N−F bond at 2. With the carbene precursor N2CH(CO2Et) N−F bond cleavage gave the Au−F bond insertion product [Au{CHF(CO2C2H5)}(SPhos)] (7). The presence of CNtBu led to Au−N cleavage at 2 and concomitant amide formation to give the cationic complex [Au(CNtBu)(SPhos)][N(F)SO2Ph)] (5), which reacted further to give FtBu as well as the cyanido complex [Au(CN)(SPhos)] (6). These results led to the development of a process for the amination of electrophilic organic substrates by transfer of the fluoroamido group NF(SO2Ph)−.