Asymmetric Büchner reaction and arene cyclopropanation via copper-catalyzed controllable cyclization of diynes

Yan-Xin Zheng; Li-Gao Liu; Tian-Qi Hu; Xiao Li; Zhou Xu; Xin Hong; Xin Lu; Bo Zhou; Long-Wu Ye

doi:10.1038/s41467-024-53605-7

Asymmetric Büchner reaction and arene cyclopropanation via copper-catalyzed controllable cyclization of diynes

Nat Commun. 2024 Oct 25;15(1):9227. doi: 10.1038/s41467-024-53605-7.

Authors

Yan-Xin Zheng^#¹, Li-Gao Liu^#², Tian-Qi Hu¹, Xiao Li¹, Zhou Xu³, Xin Hong^{4

5}, Xin Lu¹, Bo Zhou¹, Long-Wu Ye^{6

7}

Affiliations

¹ 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, China.
² Center of Chemistry for Frontier Technologies, Department of Chemistry, State Key Laboratory of Clean Energy Utilization, Zhejiang University, Hangzhou, China.
³ Jiangsu Key Laboratory of New Drug Research and Clinical Pharmacy, School of Pharmacy, Xuzhou Medical University, Xuzhou, China.
⁴ 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, China. hxchem@zju.edu.cn.
⁵ Center of Chemistry for Frontier Technologies, Department of Chemistry, State Key Laboratory of Clean Energy Utilization, Zhejiang University, Hangzhou, China. hxchem@zju.edu.cn.
⁶ 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, China. longwuye@xmu.edu.cn.
⁷ State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai, China. longwuye@xmu.edu.cn.

^# Contributed equally.

Abstract

The asymmetric Büchner reaction and related arene cyclopropanations represent one type of the powerful methods for enantioselective dearomatization. However, examples of asymmetric Büchner reactions via a non-diazo approach are quite scarce, and the related arene cyclopropanation based on alkynes has not been reported. Herein, we disclose an asymmetric Büchner reaction and the related arene cyclopropanation by copper-catalyzed controllable cyclization of N-propargyl ynamides via vinyl cation intermediates, leading to chiral tricycle-fused cycloheptatrienes and benzonorcaradienes in high yields and enantioselectivities. Importantly, this protocol represents an asymmetric arene cyclopropanation reaction of alkynes and an asymmetric Büchner reaction based on vinyl cations.