Aza enolates (also known as imine anions, enamides, metallated Schiff bases, and metalloenamines) are nitrogen analogous to enolates. When imines get treated with strong bases such as LDA, highly nucleophilic aza enolates are generated.
The major benefit of using aza enolates is that they don't undergo self-condensation (i.e. aldol reaction for aldehydes) in a basic or neutral solution, but rather they favor alkylation on the alpha-carbon. This is mainly because imines contain carbon-nitrogen double bonds unlike aldehydes, which contain oxygen-carbon double bonds. Since oxygen is more electronegative than nitrogen, it withdraws more electron density from the carbonyl carbon, inducing a greater partially positive charge on the carbon. Therefore, with more electrophilic carbon, aldehydes allow for better nucleophilic addition to the carbon on the carbon-oxygen double bond.
On the other hand, imine has less electronegative nitrogen which induces a weaker partially positive charge on the carbonyl-carbon. As a result, while imines can still react with organolithiums, they don't react with other nucleophiles (including aza enolates) to undergo nucleophilic additions.
Instead, aza enolates react similarly to enolates, forming SN2 alkylated products. Through nitrogen lone pair conjugation, β-carbon becomes a nucleophilic site, permitting aza enolates to undergo alkylation reactions. Thus, aza enolates can react with numerous electrophiles like epoxides and alkyl halides to form a new carbon-carbon bond on β-carbon.
Two potential reaction mechanisms are shown below:
Since epoxide is a three-membered ring molecule, it has a high degree of ring strain. Although the carbons in the ring system are tetrahedral, preferring 109.5 degrees between each atom, epoxide strains the ring angles into 60 degrees. To counter this effect, the nucleophilic aza enolates easily react with epoxides to reduce their ring strains.
Besides reacting with epoxides, aza enolates can also react with alkyl halides (or allyl halides as depicted above) to form a new carbon-carbon sigma bond. This reaction is one of the key steps in the synthesis of the male aggression pheromone, Oulema melanopus. Aza enolate is generated by LDA reacting with pivaldehyde, which then reacts with an alkyl halide to form an Oulema melanopus intermediate.
Aza enolates can also be formed with Grignard reagents and react with other soft electrophiles, including Michael receptors.