Meyer–Schuster rearrangement/allylic alkenylation of propynolaldehydes with olefins to synthesize skipped 1,4-dienes

Abstract

A highly efficient method for the straightforward synthesis of skipped 1,4-dienes is presented via p-TsOH·H₂O-catalyzed intramolecular intercepted Meyer–Schuster rearrangement/allylic alkenylation of propynolaldehydes with olefins in a one-pot manner. This cascade transformation is characterized by metal-free and mild conditions, extensive substrate applicability, atom economy, gram-scale production, and water as the sole by-product. Furthermore, the resulting functionalized 1,4-dienes could be derivatized by Fe(III)-promoted radical cyclization, allylic methoxylation under reductive conditions, and Pd(II)-catalyzed Sonogashira coupling.