Citation: Yixiao Zhao, Gavin Chit Tsui, Qilong Shen. Key intermediates in Cu^Ⅰ to Cu^Ⅲ catalytic cycle for ethoxycarbonyl difluoro- methylation[J]. Chinese Chemical Letters, ;2025, 36(12): 111051. doi: 10.1016/j.cclet.2025.111051 shu

Key intermediates in Cu^Ⅰ to Cu^Ⅲ catalytic cycle for ethoxycarbonyl difluoro- methylation

Yixiao Zhao ^a ,
Gavin Chit Tsui ^{b, *,} ,
Qilong Shen ^{a, *,}

a.
State Key Laboratory of Fluorine and Nitrogen Chemistry and Advanced Materials, Shanghai Institute of Organic Chemistry, University of Chinese, Academy Sciences, Chinese Academy of Sciences, Shanghai 200032, China
b.
Department of Chemistry, The Chinese University of Hong Kong, Shatin, New Territories, Hong Kong SAR, China

gctsui@cuhk.edu.hk

shenql@sioc.ac.cn

Received Date: 9 December 2024
Revised Date: 5 March 2025
Accepted Date: 6 March 2025
Available Online: 7 March 2025

Figures(10)

The active Cu(Ⅰ) species Q⁺ [Cu^Ⅰ(CF₂CO₂Et)(Cl)]^- 1a and Q⁺ [Cu^Ⅰ(CF₂CO₂Et)₂]^- 1b (Q = Ph₄P), which played an important role in the copper mediated ethoxycarbonyl difluoromethylation of organic halides, have been isolated and characterized for the first time. Stoichiometric reaction showed complex 1b is much more reactive than 1a. Furthermore, while oxidative addition of complex 1b with aryl iodide resulted in the formation of the reductive elimination product without the observation of the Cu(Ⅲ) intermediate, the oxidative addition of iodoacetronitrile to 1b successfully generated Cu(Ⅲ) intermediates that reductively eliminate to give the products. Building on the stoichiometric reaction, a copper-catalyzed ethoxycarbonyl difluoromethylation of benzylic, allylic halides was developed. Additionally, it has been found that complex 1b serves as a powerful ethoxycarbonyl difluoromethylation reagent capable of ethoxycarbonyl difluoromethylating a variety of electrophiles including (hetero)aryl electrophiles, alkyl electrophiles and acid chloride, disulfide. Moreover, the oxidative ethoxycarbonyl difluoromethylation of complex 1b with various lithium n–butyl (hetero)aryl boronic acid pinacol esters has been achieved in the presence of an oxidant.
- Cu(Ⅰ) complexes,
- Cu(Ⅲ) complexes,
- Ethoxycarbonyl difluoromethylation,
- Copper-catalyzed,
- Cross-coupling
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通讯作者: 陈斌, bchen63@163.com

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沈阳化工大学材料科学与工程学院沈阳 110142

Key intermediates in CuⅠ to CuⅢ catalytic cycle for ethoxycarbonyl difluoro- methylation

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通讯作者: 陈斌, bchen63@163.com

Key intermediates in Cu^Ⅰ to Cu^Ⅲ catalytic cycle for ethoxycarbonyl difluoro- methylation