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

Y Yan‐Xin Zheng (State Key Laboratory of Physical Chemistry of Solid Surfaces Key Laboratory of Chemical Biology of Fujian Province and College of Chemistry and Chemical Engineering Xiamen University Xiamen 361005 China) L Li‐Gao Liu (Center of Chemistry for Frontier Technologies Department of Chemistry State Key Laboratory of Clean Energy Utilization Zhejiang University Hangzhou 310027 China) Y Yu‐Yao Zhou (State Key Laboratory of Physical Chemistry of Solid Surfaces Key Laboratory of Chemical Biology of Fujian Province and College of Chemistry and Chemical Engineering Xiamen University Xiamen 361005 China) S Shu‐Ya Yang (State Key Laboratory of Physical Chemistry of Solid Surfaces Key Laboratory of Chemical Biology of Fujian Province and College of Chemistry and Chemical Engineering Xiamen University Xiamen 361005 China) X Xin‐Qi Zhu (Yunnan Key Laboratory of Modern Separation Analysis and Substance Transformation College of Chemistry and Chemical Engineering Yunnan Normal University Kunming 650500 China) X Xin Hong (State Key Laboratory of Advanced Environmental Technology, Department of Environmental Science and Engineering) B Bo Zhou L Long‐Wu Ye (State Key Laboratory of Physical Chemistry of Solid Surfaces, College of Chemistry and Chemical Engineering Xiamen University Xiamen China)

Abstract

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.

Article Details

Volume / Issue Vol. 64, Issue 38
Published September 15, 2025
ISSN 1433-7851
Publisher Wiley

Journal Info

Angewandte Chemie International Edition

Wiley

ISSN: 1433-7851 Physical Sciences

Authors (8)

Y

Yan‐Xin Zheng

State Key Laboratory of Physical Chemistry of Solid Surfaces Key Laboratory of Chemical Biology of Fujian Province and College of Chemistry and Chemical Engineering Xiamen University Xiamen 361005 China

L

Li‐Gao Liu

Center of Chemistry for Frontier Technologies Department of Chemistry State Key Laboratory of Clean Energy Utilization Zhejiang University Hangzhou 310027 China

Y

Yu‐Yao Zhou

State Key Laboratory of Physical Chemistry of Solid Surfaces Key Laboratory of Chemical Biology of Fujian Province and College of Chemistry and Chemical Engineering Xiamen University Xiamen 361005 China

S

Shu‐Ya Yang

State Key Laboratory of Physical Chemistry of Solid Surfaces Key Laboratory of Chemical Biology of Fujian Province and College of Chemistry and Chemical Engineering Xiamen University Xiamen 361005 China

X

Xin‐Qi Zhu

Yunnan Key Laboratory of Modern Separation Analysis and Substance Transformation College of Chemistry and Chemical Engineering Yunnan Normal University Kunming 650500 China

X

Xin Hong

State Key Laboratory of Advanced Environmental Technology, Department of Environmental Science and Engineering

B

Bo Zhou

L

Long‐Wu Ye

State Key Laboratory of Physical Chemistry of Solid Surfaces, College of Chemistry and Chemical Engineering Xiamen University Xiamen China