Citation: Jialin Huang, Liying Fu, Zhanyong Tang, Xiaoqiang Ma, Xingda Zhao, Depeng Zhao. Cross-coupling of trifluoromethylarenes with alkynes C(sp)-H bonds and azoles C(sp²)-H bonds via photoredox/copper dual catalysis[J]. Chinese Chemical Letters, ;2025, 36(7): 110505. doi: 10.1016/j.cclet.2024.110505 shu

Cross-coupling of trifluoromethylarenes with alkynes C(sp)-H bonds and azoles C(sp²)-H bonds via photoredox/copper dual catalysis

State Key Laboratory of Anti-infective Drug Discovery and Development, School of Pharmaceutical Sciences, Sun Yat-sen University, Guangzhou 510006, China

zhaodp5@mail.sysu.edu.cn

Received Date: 8 July 2024
Revised Date: 12 September 2024
Accepted Date: 24 September 2024
Available Online: 24 September 2024

Figures(6)

Selective defluorinative functionalization of trifluoromethylarenes (ArCF₃) to obtain the pharmaceutically common α,α-difluorobenzylic motif is an attractive and elegant synthetic route. Over the past decade, although C(sp³)-F bonds functionalization have been greatly developed, catalytic cross-coupling of trifluoromethylarenes with CH of terminal alkynes remains a challenge. Here, we report an approach to achieve Sonogashira-type cross-coupling of trifluoromethylarenes with terminal alkynes C(sp)-H bonds via photoredox and Cu/L dual catalysis. Tridentate anionic ligand is pivotal to realize this C–H sp-sp³ cross-coupling. Moreover, this unique catalytic system is also suitable for cross-coupling of C(sp³)-F bonds with azoles C(sp²)-H bonds. A series of trifluoromethylarenes, terminal alkynes and azoles with various functional groups are compatible with this protocol affording a variety of defluoroalkynylation or defluoroazolation products. Preliminary mechanistic studies indicated that deprotonated BINOL involved as a photocatalyst to activate ArCF₃ rather than a ligand to the metal.
- Defluorination,
- Photoredox,
- Copper-catalyzed,
- Cross-coupling,
- Alkynylation,
- Azolation
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通讯作者: 陈斌, bchen63@163.com

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Cross-coupling of trifluoromethylarenes with alkynes C(sp)-H bonds and azoles C(sp2)-H bonds via photoredox/copper dual catalysis

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通讯作者: 陈斌, bchen63@163.com

Cross-coupling of trifluoromethylarenes with alkynes C(sp)-H bonds and azoles C(sp²)-H bonds via photoredox/copper dual catalysis