Citation: Da-Qiu Cui, Quan-Xin Li, Jia-Bo Huang, Ying-Qi Zhang, Xuan Wang, Shao-Fei Ni, Long-Wu Ye, Bo Zhou. Atroposelective transformation of vinyl cations by chiral Brønsted acid catalysis[J]. Chinese Chemical Letters, ;2026, 37(6): 111738. doi: 10.1016/j.cclet.2025.111738 shu

Atroposelective transformation of vinyl cations by chiral Brønsted acid catalysis

Da-Qiu Cui ^a ,
Quan-Xin Li ^b ,
Jia-Bo Huang ^b ,
Ying-Qi Zhang ^a ,
Xuan Wang ^a ,
Shao-Fei Ni ^{b, c, *,} ,
Long-Wu Ye ^{a, d, e} ,
Bo Zhou ^{a, *,}

a.
State Key Laboratory of Physical Chemistry of Solid Surfaces and Key Laboratory of Chemical Biology of Fujian Province, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China
b.
College of Chemistry & Chemical Engineering and Key Laboratory for Preparation and Application of Ordered Structural Materials of Guangdong Province, Shantou University, Shantou 515063, China
c.
Chemistry and Chemical Engineering Guangdong Laboratory, Shantou 515063, China
d.
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032, China
e.
State Key Laboratory of Elemento-Organic Chemistry, Nankai University, Tianjin 300071, China

sfni@stu.edu.cn

zhoubo@xmu.edu.cn

Received Date: 5 May 2025
Revised Date: 5 August 2025
Accepted Date: 17 August 2025
Available Online: 18 August 2025

Figures(6)

Over the past decades, vinyl cations have been developed as versatile synthetic intermediates in organic chemistry, that allow the construction of various C–C and C–X bonds. However, the catalytic enantioselective transformation of vinyl cations remains one of the major challenges in asymmetric catalysis, especially for the organocatalytic enantioselective reaction. Herein, we report a chiral Brønsted acid-catalyzed atroposelective reaction of vinyl cations by combining organocatalytic diyne cyclization with C(sp²)–H functionalization of diphenols. The effective chiral induction model of vinyl cations enables the streamlined synthesis of axially chiral acyclic tetrasubstituted alkenes with the simultaneous control of chemoselectivity, regioselectivity, E/Z selectivity and enantioselectivity. Further derivatizations and applications demonstrate the potential utility of constructed axially chiral skeletons in asymmetric catalysis. Computational mechanistic studies reveal the reaction mechanism and origin of selectivities. Notably, this protocol represents the first organocatalytic asymmetric intermolecular reaction of vinyl cations, as well as the first organocatalytic enantioselective diyne cyclization.
- Axial chirality,
- Chiral Brønsted acid catalysis,
- Vinyl cations
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