Facile Approach for the Oxidative Enolate Activation of Aliphatic Aldehydes.

A proline/N-heterocyclic carbene relay catalytic strategy is developed for the oxidative enolate activation of aliphatic aldehydes. A broad scope of electrophiles including oxindole-derived pyrazolones, oxindole-derived α,β-unsaturated esters, and α,β-unsaturated imines are effective as the reactants in the asymmetric [2 + 4] cycloaddition reaction with the alkyl aldehydes bearing different substitution patterns. Structural complex multicyclic chiral products can be afforded in generally excellent yields and enantio- and diastereoselectivities through this approach under similar reaction conditions. Several of the optical pure products afforded from this protocol exhibit excellent antibacterial activities against plant pathogens and are promising in the development of novel pesticides for plant protection.