124348-40-9Relevant articles and documents
Reaction of α,β-Unsaturated Imidates with Grignard Reagents Leading to 2-Alkyl 1,3-Diimines
Inoue, Seiichi,Suzuki, Osamu,Sato, Kikumasa
, p. 1773 - 1774 (1985)
Methyl N-phenylacrylimidate (1a) reacted with alkyl- and aryl-magnesium bromides in ether at O deg C to give 2-alkyl 1,3-diketones (3a) in a good yield after aqueous work-up; methyl N-phenylcrotonimidate (1b) and N-phenylcinnamimidate (1c) with alkylmagnesium bromides furnished analogous 1,3-diketones (3) as the major products after hydrolysis of the corresponding stable diimines (2).
Direct conversion of cinnamate esters into β,β-disubstituted ketones mediated by cyano-magnesio cuprates
Genna, Douglas T.,Posner, Gary H.
, p. 5968 - 5971 (2016)
The clean synthesis of unsymmetrical ketones from carboxylic acid derivatives has been a challenge in the organic community dating back over 80 years. Herein we report the conversion of simple alkyl cinnamates to β,β-disubstituted ketones with cyano-magnesio cuprates in high yields with no observation of tertiary alcohol byproduct. The lack of tertiary alcohol is attributed to a putative enolate intermediate that serves as a ketone protecting group. A distinctive steric inhibition trend was observed related to both the size of the R group on the parent ester and the nucleophilic cuprate. Lastly, we demonstrate that this reaction can be coupled with known copper mediated allylic substitution reactions yielding β,γ-disubstituted ketone (8) from parent α-chloro-β,γ-ethylenic ester (7).
