Stereoselective allylic 1,3-dienylation of Morita-Baylis-Hillman carbonates via an alkylation-denitration sequence

A two-step, metal-free process for stereoselective allylic 1,3-dienylation of Morita-Baylis-Hillman (MBH) carbonates under mild reaction conditions has been developed. Using cyclic allylic nitro compounds as potential dienylating reagents, the transformation proceeds through tertiary amine-catalyzed allylic alkylation with MBH carbonates (14 examples, up to 94% yield), followed by AcOH-mediated denitration (12 examples, up to 87% yield), affording allylic 1,3-dienyl MBH derivatives with exclusive (E)-selectivity.

Automated summary

A two-step metal-free process has been developed for the stereoselective allylic 1,3-dienylation of Morita-Baylis-Hillman (MBH) carbonates under mild reaction conditions. This transformation involves allylic alkylation with MBH carbonates followed by denitration, resulting in allylic 1,3-dienyl MBH derivatives with exclusive (E)-selectivity.