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http://dx.doi.org/10.5012/bkcs.2012.33.8.2711

A Theoretical Study on the Alkylation of the Ambident Enolate from a Methyl Glycinate Schiff Base  

Nahm, Kee-Pyung (Department of Chemistry, Yeungnam University)
Lee, Seung-Min (Department of Chemistry, Yeungnam University)
Publication Information
Bulletin of the Korean Chemical Society / v.33, no.8, 2012 , pp. 2711-2718 More about this Journal
Abstract
The alkylation of the ambident enolates of a methyl glycinate Schiff base with ethyl chloride was studied at B3LYP and MP2 levels with $6-31+G^*$ basis set. The free (E)-enolates and (Z)-enolate are similar in energy and geometry. The transition states for the alkylation of the free (E)/(Z)-enolate with ethyl chloride have similar energy barriers of ~13 kcal/mol. However, with a lithium ion, the (E)-enolate behaves as an ambident enolate and makes a cyclic lithium-complex in bidentate pattern which is more stable by 11-23 kcal/mol than the (Z)-enolate-lithium complexes. And the TS for the alkylation of (E)-enolate-lithium complex coordinated with one methyl ether is lower in energy than those from (Z)-enolate-lithium complexes by 4.3-7.3 kcal/mol. Further solvation model (SCRF-CPCM) and reaction coordinate (IRC) were studied. This theoretical study suggests that the alkylation of ambident enolates proceeds with stable cyclic bidentate complexes in the presence of metal ion and solvent.
Keywords
Ambident enolate; Enolate alkylation; Density functional theory (DFT);
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