Enhancing Metalating Efficiency of the Sodium Amide NaTMP in Arene Borylation Applications.

ABSTRACT: Though LiTMP (TMP=2,2',6,6'-tetramethylpiperidide) is a commonly used amide, surprisingly the heavier NaTMP has hardly been utilised. Here, by mixing NaTMP with tridentate donor PMDETA (N,N,N',N'',N''-pentamethyldiethylenetriamine), we provide structural, and mechanistic insights into the sodiation of non-activated arenes (e.g. anisole and benzene). While these reactions are low yielding, adding B(OiPr)₃ has a profound effect, not only by intercepting the C_Ar -Na bond, but also by driving the metalation reaction towards quantitative formation of more stabilized sodium aryl boronates. Demonstrating its metalating power, regioselective C2-metalation/borylation of naphthalene has been accomplished contrasting with single-metal based protocols which are unselective and lo

SUBMITTER: Bole LJ 

PROVIDER: S-EPMC9323492 | biostudies-literature | 2022 Jun

REPOSITORIES: biostudies-literature