Abstract Catalytic asymmetric 2 + 2 + 2 cycloaddition of diynes represents an efficient and atom‐economical strategy for the assembly of valuable chiral cyclic targets in a single step. However, this strategy traditionally relies on the cyclometallation process. Moreover, there are no versatile asymmetric 2 + 2 + 2 cycloaddition methods for diynes that are compatible with C─C double/triple bonds and C─X double bonds. Here, we disclose a copper‐catalyzed asymmetric 2 + 2 + 2 cycloaddition of diynes via vinyl cations. This universal 2 + 2 + 2 cycloaddition is suitable for the asymmetric cycloaddition of diynes with various C─C double/triple bonds and C─X double bonds, leading to a range of valuable chiral hexahydropyrrolocarbazoles, tetrahydropyrrolocarbazoles, and tetrahydropyran4,3‐bindoles in generally excellent yields with excellent diastereo‐ and enantioselectivities. Importantly, this protocol features the first asymmetric 2 + 2 + 2 cycloaddition via vinyl cations, and constitutes the first construction of carbon stereocenters in triyne cyclization.
Zheng et al. (2025) studied this question.