Citation: Huidan Geng, Jiuwei Nie, Wei Chen, Chong Zhao, Zikun Yao, Hui Wang, Jiquan Zhang, Lei Tang, Yuanyong Yang. A σ-π bond interchange assisted σ-π cross-metathesis reaction for nonoxidative conversion of methyl ketones to carboxylic acids[J]. Chinese Chemical Letters, ;2026, 37(4): 111277. doi: 10.1016/j.cclet.2025.111277 shu

A σ-π bond interchange assisted σ-π cross-metathesis reaction for nonoxidative conversion of methyl ketones to carboxylic acids

Huidan Geng ^{a, b, 1} ,
Jiuwei Nie ^{a, 1} ,
Wei Chen ^{a, 1} ,
Chong Zhao ^{a, 1} ,
Zikun Yao ^a ,
Hui Wang ^a ,
Jiquan Zhang ^a ,
Lei Tang ^{a, *,} ,
Yuanyong Yang ^{a, *,}

a.
State Key Laboratory of Discovery and Utilization of F unctional Components in Traditional Chinese Medicine & School of Pharmaceutical Sciences, Guizhou Medical University, Guiyang 550014, China
b.
Liupanshui Inspection and Testing Center, Liupanshui 553000, China

312854015@qq.com

yangyuanyong@gmc.edu.cn

Received Date: 17 January 2025
Revised Date: 24 April 2025
Accepted Date: 29 April 2025
Available Online: 30 April 2025

Figures(10)

Selective activation of C-C bonds via molecular editing is a fundamental challenge in organic synthesis. Among the various strategies, metathesis reactions have emerged as powerful tools for constructing new molecular architectures due to their well-established mechanisms. However, these reactions have largely been limited to the same types of covalent bonds, such as σ-σ or π-π bonds, leaving σ-π cross-metathesis reactions unexplored. Perhaps the bond redistribution between the σ and π bonds is highly difficult due to the lack of p orbital in σ bonds. Herein, we report the first example of a transition metal-free σ-π cross-metathesis reaction that converts methyl ketones into the corresponding carboxylic acids along with the formation of 11H-benzo[b]fluoren-11-one. A comprehensive mechanistic investigation, supported by DFT calculations, was conducted to elucidate the unique reaction pathway. This study not only provides compelling evidence for the first σ-π cross-metathesis reaction but also demonstrates the formation of a key oxetan-2-olate intermediate and its utility in organic transformations. This novel concept and strategy expand the scope of traditional metathesis reactions, offering new possibilities for selective C-C bond activation in a redox-neutral manner.
- Cross-metathesis reaction,
- Nonoxidative,
- Ketones to carboxylic acid,
- Transition metal-free,
- C-C bond activation
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