Metallation chemistry, the classical C-H bond activation methodology, has undergone a remarkable step change in recent times. The key is to use bimetallic reagents. While organomagnesium and diorganozinc compounds are relatively poor deprotonating agents in their own right, activated by an alkali metal, they can be transformed into super reactive bases. At the core of these advances has been the sterically demanding 2,2,6,6-tetramethylpiperidide (TMP) ligand, typified by its presence in the Knochel-Hauser base, (TMP)MgCl.LiCl or our own sodium zincate (TMEDA)Na(TMP)(tBu)Zn(tBu). However, the precursor amine TMP(H) is expensive and so a major challenge is to find a cheaper alternative.This presentation will focus on our studies of the related but much cheaper amine cis-2, 6 dimethylpiperidine, DMP. We discuss the synthesis and structures of the new DMP zincate bases (TMEDA)Li(DMP)(R)Zn(R) (where R= tBu or Et), their solution chemistry, and their applications for the selective deprotonation of various aromatic and heteroaromatic substrates.

<i>Cis</i>-2,6-dimethylpiperidide (DMP) in bimetallic bases:  A cheaper alternative to 2,2,6,6-tetramethylpiperidide (TMP)

245th National Meeting (2013)

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Cis-2,6-dimethylpiperidide (DMP) in bimetallic bases: A cheaper alternative to 2,2,6,6-tetramethylpiperidide (TMP)