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

The Au I complex [Au{N(F)SO 2 Ph}(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 N 2 CH(CO 2 Et) N−F bond cleavage gave the Au−F bond insertion product [Au{CHF(CO 2 C 2 H 5 )}(SPhos)] ( 7 ). The presence of CN t Bu led to Au−N cleavage at 2 and concomitant amide formation to give the cationic complex [Au(CN t Bu)(SPhos)][N(F)SO 2 Ph)] ( 5 ), which reacted further to give F t Bu 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(SO 2 Ph) − .