Alkali Metal Effects in Trans-Metal-Trapping (TMT): Comparing LiTMP with NaTMP in Cooperative MTMP/Ga(CH₂SiMe₃)₃ Meta­lation Reactions

Published as part of the 50 Years SYNTHESIS – Golden Anniversary Issue

Abstract

Stepwise metalation and trapping, so called trans-metal-trapping (TMT), of anisole is studied using LiTMP as base and Ga(CH₂SiMe₃)₃ as trap. The isolated ‘trapped’ intermediate is also assessed in C–C bond forming reactions, highlighting the inherent advantages and remaining challenges of this system. The same base trap mixture is found to metallate N–Me bonds of the diamines TMEDA and PMDETA. Comparative studies replacing LiTMP by NaTMP have found significant alkali metal effects on the extent of both base-trap cocomplexation and onward reactivities of TMT products.

Key words

metalation - gallium trans-metal-trapping - carbanions - cooperative effects - lithium - sodium

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