Abstract

In general, the design of complex polycycles from simple building blocks is challenging and requires many reaction steps. Herein, we present that complex polycycles can be synthesized starting from two alkyne building blocks in a one‐pot reaction using gold(I) as catalyst, in yields up to 77 %. Mechanistically, the process can be described as cascade reaction in two steps: first, the allene is formed by gold(I)‐catalyzed dearomatization, second, the desired product is then obtained by allene–diene–alkyne coupling. Quantum chemical investigations confirm the assumed mechanism. In sum, five new C–C bonds are built in one sweep, which is extraordinary since non‐identical building blocks are combined in this reaction. The introduced new allene–diene–alkyne coupling reaction paves the way for several new syntheses of cycles and polycycles considering potential intermolecular reactions.

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