Abstract

AbstractWe report herein a gold and palladium sequential catalysis system to access furan‐fused nine‐membered heterocycles in high efficiency and enantioselectivity. In this one‐pot procedure, easily accessible enynamides undergo cyclization to generate azadienes in situ that participate in enantioselective formal [5+4] cycloaddition with vinyl ethylene carbonates. Conformation‐controlled highly diastereoselective derivatizations of these medium‐sized rings, coupled with oxidative furan cleavage, have enabled the access to diverse densely‐functionalized nine‐membered lactams.

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