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26.10.2.1.2.3 Variation 3: With Amides or Nitriles

DOI: 10.1055/sos-SD-026-01067

Chataigner, I.; Harrison-Marchand, A.; Maddaluno, J.Science of Synthesis, (2005261153.

Carboxamides and nitriles are excellent electrophiles that are widely used as acylating agents, although their reactions with alkyllithium or Grignard reagents can provide ketones, tertiary alcohols, enamines, or amino alcohols, depending on the structure of the amide. In the specific case of the acylation of esters and related compounds, resorting to amides facilitates the differentiation between the electronic natures of the two carbonyl functions and avoids the production of mixtures of products, as obtained by acylating an ester enolate with another ester (see Section 26.10.2.1.2.2). The self-condensation of carboxamides can, however, be deliberately promoted by using organometallic reagents such as butyllithium or Grignard reagents.[‌307‌] What makes amides particularly suitable as acylating agents is their capacity to avoid a second addition of the enolate to the newly formed ketone, probably because of the stability of the intermediate α-aminoalcoholate in the reaction medium.

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