Lipshutz-type bis(amido)argentates for directed argentation.

Bis(amido)argentate (TMP)Ag(CN)Li (, TMP-Ag-ate; TMP = 2,2,6,6-tetramethylpiperidido) was designed as a tool for chemoselective aromatic functionalization unprecedented directed argentation (DAg). X-Ray crystallographic analysis showed that takes a structure analogous to that of the corresponding Lipshutz cuprate. DAg with this TMP-Ag-ate afforded multifunctional aromatics in high yields in processes that exhibited high chemoselectivity and compatibility with a wide range of functional groups. These included organometallics- and transition metal-susceptible substituents such as methyl ester, aldehyde, vinyl, iodo, (trifluoromethanesulfonyl)oxy and nitro groups. The arylargentates displayed good reactivity with various electrophiles. Chalcogen (S, Se, and Te) installation and azo coupling reactions also proceeded efficiently.