Copper‐Catalyzed Asymmetric [2 + 2 + 2] Cycloaddition of Diynes via Vinyl Cations

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Angewandte Chemie Int Ed, Wiley-VCH

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Angewandte Chemie International Edition, EarlyView.

A copper‐catalyzed asymmetric [2 + 2 + 2] cycloaddition of diynes via vinyl cations has been disclosed, enabling the efficient and practical synthesis of valuable chiral polycyclic indoles with excellent yields and unprecedented diastereo‐ and enantioselectivities. This reaction features the first asymmetric [2 + 2 + 2] cycloaddition via vinyl cations and the first enantioselective triyne cyclization for the construction of carbon stereocenters. 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 tetrahydropyran[4,3‐b]indoles 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.

A copper-catalyzed asymmetric [2 + 2 + 2] cycloaddition of diynes via vinyl cations has been disclosed, enabling the efficient and practical synthesis of valuable chiral polycyclic indoles with excellent yields and unprecedented diastereo- and enantioselectivities. This reaction features the first asymmetric [2 + 2 + 2] cycloaddition via vinyl cations and the first enantioselective triyne cyclization for the construction of carbon stereocenters.

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 tetrahydropyran[4,3-b]indoles 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.

Yan‐Xin Zheng, Li‐Gao Liu, Yu‐Yao Zhou, Shu‐Ya Yang, Xin‐Qi Zhu, Xin Hong, Bo Zhou, Long‐Wu Ye

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