syn-Fluoro- and -Oxy-trifluoromethylation of ArylacetylenesClick to copy article linkArticle link copied!
Abstract

One-step concurrent fluoro-trifluoromethylation across the triple bond of arylacetylenes in a syn mode is enabled by the collaboration of (phen)CuIII(CF3)3 and CsF that produces chemo-, regio-, and stereoselectively (Z)-α-fluoro-β-CF3 styrenes. This method can be extended to achieve syn-oxy-trifluoromethylation and syn-aryl-trifluoromethylation of alkynes using phenoxides, alkoxides, or phenylboronic acid in place of CsF. It opens up new opportunities for preparing various functionalized trifluoromethylated Z-alkenes and demonstrates the potential of Cu(III)–CF3 complexes in organic synthesis.
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- Xiaoxue Hu, Yanzhao Wang, Shibo Xu, Jingjing Wu, Fanhong Wu. Visible Light-Induced Copper-Catalyzed Regio- and Stereoselective Difluoroalkylthiocyanation of Alkynes. The Journal of Organic Chemistry 2024, 89
(12)
, 9118-9124. https://doi.org/10.1021/acs.joc.4c00834
- Dou-Dou Chen, Song-Lin Zhang. Dual Oxidation of Epoxides with a High-Valent Cu(III)–CF3 Compound and DMSO to Access 1,2-Diketones. The Journal of Organic Chemistry 2023, 88
(24)
, 16735-16741. https://doi.org/10.1021/acs.joc.3c01160
- Jinfeng Huang, Yimin Jia, Xiangyu Li, Jianli Duan, Zhong-Xing Jiang, Zhigang Yang. Halotrifluoromethylation of 1,3-Enynes: Access to Tetrasubstituted Allenes. Organic Letters 2021, 23
(6)
, 2314-2319. https://doi.org/10.1021/acs.orglett.1c00449
- Chengwen Li, Li Xue, Jiaxin Zhou, Yilin Zhao, Guifang Han, Jingli Hou, Yuguang Song, Yangping Liu. Copper-Catalyzed Trifluoromethylation of Ynones Coupled with Dearomatizing Spirocyclization of Indoles: Access to CF3-Containing Spiro[cyclopentane-1,3′-indole]. Organic Letters 2020, 22
(8)
, 3291-3296. https://doi.org/10.1021/acs.orglett.0c01097
- Zhenhua Liu, Lin Yang, Kaining Zhang, Wanjiao Chen, Tian Yu, Lianxiao Wang, Wen Gao, Bo Tang. Copper-Catalyzed Disulfonation of Terminal Alkynes with Sodium Arylsulfinates. Organic Letters 2020, 22
(5)
, 2081-2086. https://doi.org/10.1021/acs.orglett.0c00575
- Song-Lin Zhang, Jia-Jia Dong. Hydrogen-Bonding-Assisted α-F Elimination from Cu–CF3 for in Situ Generation of R3N·HF Reagents: Reaction Design and Applications. Organic Letters 2019, 21
(17)
, 6893-6896. https://doi.org/10.1021/acs.orglett.9b02516
- Muhammad Israr, Haigen Xiong, Yajun Li, Hongli Bao. Copper(I)-Catalyzed Cyanoperfluoroalkylation of Alkynes. Organic Letters 2019, 21
(17)
, 7078-7083. https://doi.org/10.1021/acs.orglett.9b02648
- Song-Lin Zhang, Chang Xiao. Cu(III)–CF3 Complex Enabled Unusual (Z)-Selective Hydro-trifluoromethylation of Terminal Alkynes. The Journal of Organic Chemistry 2018, 83
(18)
, 10908-10915. https://doi.org/10.1021/acs.joc.8b01586
- Yu An, Xiao-Bo Tang, Dong-Wei Sun, Ting-Ting Meng, Bo Zhao, Sheng Han, Zhi-Qiang Yang, Wei Zhang, Nian Tang, Ji-Jun Zeng, Jian Lu. Stereoselective synthetic approach toward β-trifluoromethyl vinyl ethers and diethers
via
reaction of (
E
)-1,2-dichloro-3,3,3-trifluoroprop-1-ene with phenols. Organic & Biomolecular Chemistry 2024, 22
(41)
, 8344-8354. https://doi.org/10.1039/D4OB01254B
- Yi‐Feng Hou, Song‐Lin Zhang. Cu(III)‐CF
3
Compound‐Activated DMSO: An Efficient Oxidizing Reagent to Convert Alcohols to Ketones. European Journal of Organic Chemistry 2024, 27
(22)
https://doi.org/10.1002/ejoc.202400097
- E. Ali McKnight, Dusty Cadwallader, Christine M. Le. Carbofluorination of π‐Bonds and Related Reactions Involving Tandem C−C/C−F Bond Formation. European Journal of Organic Chemistry 2024, 27
(19)
https://doi.org/10.1002/ejoc.202300017
- Daniel Joven‐Sancho, Andrea Echeverri, Nathalie Saffon‐Merceron, Julia Contreras‐García, Noel Nebra. An Organocopper(III) Fluoride Triggering C−CF
3
Bond Formation. Angewandte Chemie 2024, 136
(11)
https://doi.org/10.1002/ange.202319412
- Daniel Joven‐Sancho, Andrea Echeverri, Nathalie Saffon‐Merceron, Julia Contreras‐García, Noel Nebra. An Organocopper(III) Fluoride Triggering C−CF
3
Bond Formation. Angewandte Chemie International Edition 2024, 63
(11)
https://doi.org/10.1002/anie.202319412
- Vladimir Motornov, Martin Procházka, Nora Alpuente, Pedro Salvador, Petr Slavíček, Blanka Klepetářová, Xavi Ribas, Petr Beier. Introducing Weakly Ligated Tris(trifluoromethyl)copper(III). ChemistryEurope 2024, 2
(2)
https://doi.org/10.1002/ceur.202400004
- Vladimir Motornov, Blanka Klepetářová, Petr Beier. Cu(III) Trifluoromethyl Complexes with 1,3‐Diketonate Ligands and Their Versatile Reactivity in C−H Trifluoromethylation. Advanced Synthesis & Catalysis 2023, 365
(17)
, 2858-2864. https://doi.org/10.1002/adsc.202300695
- Dou‐Dou Chen, Song‐Lin Zhang. Geminal/Vicinal Amino‐ and Oxy‐Trifluoromethylation of
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3
Compounds. Advanced Synthesis & Catalysis 2023, 365
(9)
, 1425-1431. https://doi.org/10.1002/adsc.202300182
- Zhen‐Mei Zheng, Ning Chen, Ming‐Suo Dai, Song‐Lin Zhang. Base‐Controlled Chemoselective Reaction of High‐Valent Cu(III)−CF
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(8)
, 1262-1267. https://doi.org/10.1002/adsc.202300017
- Shintaro Kawamura, Pablo Barrio, Santos Fustero, Jorge Escorihuela, Jianlin Han, Vadim A. Soloshonok, Mikiko Sodeoka. Evolution and Future of Hetero‐ and Hydro‐Trifluoromethylations of Unsaturated C−C Bonds. Advanced Synthesis & Catalysis 2023, 365
(4)
, 398-462. https://doi.org/10.1002/adsc.202201268
- Ming-Suo Dai, Zhen-Mei Zheng, Song-Lin Zhang. High-valent Cu(
iii
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3
compound-mediated esterification reaction. Organic & Biomolecular Chemistry 2023, 21
(5)
, 935-939. https://doi.org/10.1039/D2OB02166H
- Ning Chen, Song‐Lin Zhang. Selective Intermolecular Dual Amino‐Trifluoromethylation of Alkenes by High‐Valent Cu(III)−CF
3
Compounds. Advanced Synthesis & Catalysis 2022, 364
(22)
, 3941-3947. https://doi.org/10.1002/adsc.202200945
- Hao‐Ran Zhang, Cong‐Cong Feng, Ning Chen, Song‐Lin Zhang. Direct Arene Trifluoromethylation Enabled by a High‐Valent Cu
III
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3
Compound. Angewandte Chemie 2022, 134
(40)
https://doi.org/10.1002/ange.202209029
- Hao‐Ran Zhang, Cong‐Cong Feng, Ning Chen, Song‐Lin Zhang. Direct Arene Trifluoromethylation Enabled by a High‐Valent Cu
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3
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(40)
https://doi.org/10.1002/anie.202209029
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(23)
, 7221. https://doi.org/10.3390/molecules26237221
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(20)
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(13)
, 151693. https://doi.org/10.1016/j.tetlet.2020.151693
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(4)
, 795-800. https://doi.org/10.1002/adsc.201901405
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(23)
, 5305-5310. https://doi.org/10.1002/adsc.201901105
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(8)
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- Chang Xiao, Hai‐Xing Wan, Song‐Lin Zhang. Regio‐ and Stereoselective Vicinal
syn
‐Arylation‐Trifluoromethylation of Terminal Arylacetylenes. Asian Journal of Organic Chemistry 2019, 8
(5)
, 654-657. https://doi.org/10.1002/ajoc.201800432
- Song-Lin Zhang, Chang Xiao, Hai-Xing Wan, Xiaoming Zhang. General and selective
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-carboxylation-trifluoromethylation of terminal alkynes: application to the late-stage modification of dehydrocholic acid. Chemical Communications 2019, 55
(28)
, 4099-4102. https://doi.org/10.1039/C9CC01173K
- Jinqiang Kuang, Yuanzhi Xia, An Yang, Heng Zhang, Chenliang Su, Daesung Lee. Copper-catalyzed aminothiolation of terminal alkynes with tunable regioselectivity. Chemical Communications 2019, 55
(12)
, 1813-1816. https://doi.org/10.1039/C8CC09122F
- Chang Xiao, Song-Lin Zhang. Isolation of OH-bridged Ag(
i
)/Cu(
iii
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i
)/Cu(
iii
) trifluoromethyl complexes with monophosphines. Dalton Transactions 2019, 48
(3)
, 848-853. https://doi.org/10.1039/C8DT03876G
- Liang Liu, Zhenfeng Xi. Organocopper(III) Compounds with Well‐defined Structures Undergo Reductive Elimination to Form C—C or C–Heteroatom Bonds. Chinese Journal of Chemistry 2018, 36
(12)
, 1213-1221. https://doi.org/10.1002/cjoc.201800365
- Song-Lin Zhang, Chang Xiao, Hai-Xing Wan. Diverse copper(
iii
) trifluoromethyl complexes with mono-, bi- and tridentate ligands and their versatile reactivity. Dalton Transactions 2018, 47
(14)
, 4779-4784. https://doi.org/10.1039/C8DT00291F
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