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Csp3–Csp3 Bond-Forming Reductive Elimination from Well-Defined Copper(III) Complexes

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    Csp3–Csp3 Bond-Forming Reductive Elimination from Well-Defined Copper(III) Complexes
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    • Matthew Paeth
      Matthew Paeth
      Department of Chemistry and Biochemistry, Miami University, Oxford, Ohio 45056, United States
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    • Sam B. Tyndall
      Sam B. Tyndall
      Department of Chemistry and Biochemistry, Miami University, Oxford, Ohio 45056, United States
      More by Sam B. Tyndall
    • Liang-Yu Chen
      Liang-Yu Chen
      Department of Chemistry, National Cheng Kung University, Tainan 701, Taiwan
      More by Liang-Yu Chen
    • Jia-Cheng Hong
      Jia-Cheng Hong
      Department of Chemistry, National Cheng Kung University, Tainan 701, Taiwan
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    • William P. Carson
      William P. Carson
      Department of Chemistry and Biochemistry, Miami University, Oxford, Ohio 45056, United States
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    • Xingwu Liu
      Xingwu Liu
      State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan, Shanxi 030001, P. R. China
      National Energy Center for Coal to Liquids, Synfuels China Technology Co., Ltd, Beijing 101400, P. R. China
      More by Xingwu Liu
      Orcidhttp://orcid.org/0000-0002-8564-1151
    • Xiaodong Sun
      Xiaodong Sun
      State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan, Shanxi 030001, P. R. China
      National Energy Center for Coal to Liquids, Synfuels China Technology Co., Ltd, Beijing 101400, P. R. China
      More by Xiaodong Sun
    • Jinjia Liu
      Jinjia Liu
      State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan, Shanxi 030001, P. R. China
      National Energy Center for Coal to Liquids, Synfuels China Technology Co., Ltd, Beijing 101400, P. R. China
      More by Jinjia Liu
    • Kundi Yang
      Kundi Yang
      Department of Chemistry and Biochemistry, Miami University, Oxford, Ohio 45056, United States
      More by Kundi Yang
    • Elizabeth M. Hale
      Elizabeth M. Hale
      Department of Chemistry and Biochemistry, Miami University, Oxford, Ohio 45056, United States
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    • David L. Tierney
      David L. Tierney
      Department of Chemistry and Biochemistry, Miami University, Oxford, Ohio 45056, United States
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    • Bin Liu
      Bin Liu
      A Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of Ministry of Education, Shaanxi Key Laboratory of Physico-Inorganic Chemistry, College of Chemistry and Materials Science, Northwest University, Xi’an 710127, P. R. China
      More by Bin Liu
    • Zhi Cao*
      Zhi Cao
      State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan, Shanxi 030001, P. R. China
      National Energy Center for Coal to Liquids, Synfuels China Technology Co., Ltd, Beijing 101400, P. R. China
      *[email protected]
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    • Mu-Jeng Cheng
      Mu-Jeng Cheng
      Department of Chemistry, National Cheng Kung University, Tainan 701, Taiwan
      More by Mu-Jeng Cheng
      Orcidhttp://orcid.org/0000-0002-8121-0485
    • William A. Goddard III*
      William A. Goddard III
      Materials and Process Simulation Center (MC 139-74), California Institute of Technology, Pasadena, California 91125, United States
      *[email protected]
      More by William A. Goddard III
      Orcidhttp://orcid.org/0000-0003-0097-5716
    • Wei Liu*
      Wei Liu
      Department of Chemistry and Biochemistry, Miami University, Oxford, Ohio 45056, United States
      *[email protected]
      More by Wei Liu
      Orcidhttp://orcid.org/0000-0001-6249-3179
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    Journal of the American Chemical Society

    Cite this: J. Am. Chem. Soc. 2019, 141, 7, 3153–3159
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    https://doi.org/10.1021/jacs.8b12632
    Published January 25, 2019
    Copyright © 2019 American Chemical Society
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    Abstract

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    Carbon–carbon bond-forming reductive elimination from elusive organocopper(III) complexes has been considered the key step in many copper-catalyzed and organocuprate reactions. However, organocopper(III) complexes with well-defined structures that can undergo reductive elimination are extremely rare, especially for the formation of Csp3–Csp3 bonds. We report herein a general method for the synthesis of a series of [alkyl-CuIII-(CF3)3]− complexes, the structures of which have been unequivocally characterized by NMR spectroscopy, mass spectrometry, and X-ray crystal diffraction. At elevated temperature, these complexes undergo reductive elimination following first-order kinetics, forming alkyl-CF3 products with good yields (up to 91%). Both kinetic studies and DFT calculations indicate that the reductive elimination to form Csp3–CF3 bonds proceeds through a concerted transition state, with a ΔH⧧ = 20 kcal/mol barrier.

    Copyright © 2019 American Chemical Society

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    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/jacs.8b12632.

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    62. 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
    63. Lingfeng Yin, Wei Liu. Stable oganocopper(III) complexes generated via oxidative addition. Science Bulletin 2024, 69 (3) , 288-289. https://doi.org/10.1016/j.scib.2023.12.020
    64. P. Chen, G. Liu. 1.5 Radical Trifluoromethylation. 2024https://doi.org/10.1055/sos-SD-243-00226
    65. Pinar Alayoglu, Tieyan Chang, Connly Yan, Yu‐Sheng Chen, Neal P. Mankad. Uncovering a CF 3 Effect on X‐ray Absorption Energies of [Cu(CF 3 ) 4 ] − and Related Copper Compounds by Using Resonant Diffraction Anomalous Fine Structure (DAFS) Measurements**. Angewandte Chemie 2023, 135 (51) https://doi.org/10.1002/ange.202313744
    66. Pinar Alayoglu, Tieyan Chang, Connly Yan, Yu‐Sheng Chen, Neal P. Mankad. Uncovering a CF 3 Effect on X‐ray Absorption Energies of [Cu(CF 3 ) 4 ] − and Related Copper Compounds by Using Resonant Diffraction Anomalous Fine Structure (DAFS) Measurements**. Angewandte Chemie International Edition 2023, 62 (51) https://doi.org/10.1002/anie.202313744
    67. En Cao, Mengtao Sun. Spectral Physics of Stable Cu(III) Produced by Oxidative Addition of an Alkyl Halide. International Journal of Molecular Sciences 2023, 24 (21) , 15694. https://doi.org/10.3390/ijms242115694
    68. Yongrui Luo, Yuli Li, Jian Wu, Xiao-Song Xue, John F. Hartwig, Qilong Shen. Oxidative addition of an alkyl halide to form a stable Cu(III) product. Science 2023, 381 (6662) , 1072-1079. https://doi.org/10.1126/science.adg9232
    69. Luca Demonti, Daniel Joven‐Sancho, Noel Nebra. Cross‐Coupling Reactions Enabled by Well‐Defined Ag(III) Compounds: Main Focus on Aromatic Fluorination and Trifluoromethylation. The Chemical Record 2023, 23 (9) https://doi.org/10.1002/tcr.202300143
    70. Tobias Michael Milzarek, Jerome Waser. Synthese von Trifluormethylierten Alkenen: hypervalentes Iod trifft hochvalentes Kupfer. Angewandte Chemie 2023, 135 (33) https://doi.org/10.1002/ange.202306128
    71. Tobias Michael Milzarek, Jerome Waser. Synthesis of Trifluoromethylated Alkenes: Hypervalent Iodine Meets High‐Valent Copper. Angewandte Chemie International Edition 2023, 62 (33) https://doi.org/10.1002/anie.202306128
    72. Bastian Zimmer, Thomas Auth, Konrad Koszinowski. Unimolecular Reactivity of [Cu(R)(CF 3 ) 3 ] − Complexes (R=Organyl): Stepwise versus Concerted Mechanism in Copper‐Mediated Trifluoromethylation. Chemistry – A European Journal 2023, 29 (41) https://doi.org/10.1002/chem.202300725
    73. Hoorub Ahmad, Muhammad Bilal, Tahir Maqbool, Nasir Rasool, Syed Adnan Ali Shah, Zainul Amiruddin Zakaria. Recent advances on copper-catalyzed asymmetric synthesis and their potential biological applications. Journal of Saudi Chemical Society 2023, 27 (4) , 101658. https://doi.org/10.1016/j.jscs.2023.101658
    74. Dou‐Dou Chen, Song‐Lin Zhang. Geminal/Vicinal Amino‐ and Oxy‐Trifluoromethylation of ortho ‐Ethynyl Anilines and Phenols by Cu(III)−CF 3 Compounds. Advanced Synthesis & Catalysis 2023, 365 (9) , 1425-1431. https://doi.org/10.1002/adsc.202300182
    75. Sergey S. Lunkov, Artem A. Zemtsov, Vitalij V. Levin, Alexander D. Dilman. Photocatalytic reduction of fluoroalkyl-substituted alcohols activated by pentafluoropyridine. Mendeleev Communications 2023, 33 (3) , 387-389. https://doi.org/10.1016/j.mencom.2023.04.028
    76. Zhen‐Mei Zheng, Ning Chen, Ming‐Suo Dai, Song‐Lin Zhang. Base‐Controlled Chemoselective Reaction of High‐Valent Cu(III)−CF 3 Compounds with Anilines: Access to Formamides or Hydrazines. Advanced Synthesis & Catalysis 2023, 365 (8) , 1262-1267. https://doi.org/10.1002/adsc.202300017
    77. Fei Cong, Riccardo S. Mega, Jinhong Chen, Craig S. Day, Ruben Martin. Trifluoromethylation of Carbonyl and Unactivated Olefin Derivatives by C( sp 3 )−C Bond Cleavage. Angewandte Chemie 2023, 135 (15) https://doi.org/10.1002/ange.202214633
    78. Fei Cong, Riccardo S. Mega, Jinhong Chen, Craig S. Day, Ruben Martin. Trifluoromethylation of Carbonyl and Unactivated Olefin Derivatives by C( sp 3 )−C Bond Cleavage. Angewandte Chemie International Edition 2023, 62 (15) https://doi.org/10.1002/anie.202214633
    79. Ming-Suo Dai, Zhen-Mei Zheng, Song-Lin Zhang. High-valent Cu( iii )–CF 3 compound-mediated esterification reaction. Organic & Biomolecular Chemistry 2023, 21 (5) , 935-939. https://doi.org/10.1039/D2OB02166H
    80. Jason Shearer, Dovydas Vasiliauskas, Kyle M. Lancaster. Bonding and the role of electrostatics in driving C–C bond formation in high valent organocopper compounds. Chemical Communications 2022, 59 (1) , 98-101. https://doi.org/10.1039/D2CC05865K
    81. Gordon Jacob Boehlich, Hannes Sterzel, Julia Rehbein, Nina Schützenmeister. Efficient Copper‐Catalyzed Highly Stereoselective Synthesis of Unprotected C ‐Acyl Manno‐, Rhamno‐ and Lyxopyranosides. Chemistry – A European Journal 2022, 28 (71) https://doi.org/10.1002/chem.202202619
    82. 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
    83. Hao‐Ran Zhang, Cong‐Cong Feng, Ning Chen, Song‐Lin Zhang. Direct Arene Trifluoromethylation Enabled by a High‐Valent Cu III −CF 3 Compound. Angewandte Chemie 2022, 134 (40) https://doi.org/10.1002/ange.202209029
    84. Hao‐Ran Zhang, Cong‐Cong Feng, Ning Chen, Song‐Lin Zhang. Direct Arene Trifluoromethylation Enabled by a High‐Valent Cu III −CF 3 Compound. Angewandte Chemie International Edition 2022, 61 (40) https://doi.org/10.1002/anie.202209029
    85. Isaac F. Leach, Remco W. A. Havenith, Johannes E. M. N. Klein. Revisiting Formal Copper(III) Complexes: Bridging Perspectives with Quasi ‐ d 10 Configurations. European Journal of Inorganic Chemistry 2022, 2022 (27) https://doi.org/10.1002/ejic.202200247
    86. Ziwei Luo, Gavin Chit Tsui. Radical cyclization/bis(pentafluoroethylation) of 1,6-dienes using HCF 2 CF 3 -derived CuCF 2 CF 3. Organic Chemistry Frontiers 2022, 9 (18) , 4969-4974. https://doi.org/10.1039/D2QO00919F
    87. Ernesto Rufino‐Felipe, Hugo Valdés, David Morales‐Morales. C−S Cross‐Coupling Reactions Catalyzed by Well‐Defined Copper and Nickel Complexes. European Journal of Organic Chemistry 2022, 2022 (31) https://doi.org/10.1002/ejoc.202200654
    88. Guangyu Wang, Man Li, Xuebing Leng, Xiaosong Xue, Qilong Shen. Neutral Five‐Coordinate Arylated Copper( III ) Complex: Key Intermediate in Copper‐Mediated Arene Trifluoromethylation. Chinese Journal of Chemistry 2022, 40 (16) , 1924-1930. https://doi.org/10.1002/cjoc.202200230
    89. Thomas Auth, Christopher J. Stein, Richard A. J. O'Hair, Konrad Koszinowski. Origin of the different reactivity of the high‐valent coinage‐metal complexes [RCu iii Me 3 ] − and [RAg iii Me 3 ] − (R=allyl)**. Chemistry – A European Journal 2022, 28 (7) https://doi.org/10.1002/chem.202103130
    90. Hugo Valdés, Xavi Ribas. Organometallic Complexes of Copper. 2022, 1-31. https://doi.org/10.1016/B978-0-12-820206-7.00124-4
    91. Aijie Cai, Wenhao Yan, Chao Wang, Wei Liu. Copper‐Catalyzed Difluoromethylation of Alkyl Iodides Enabled by Aryl Radical Activation of Carbon–Iodine Bonds. Angewandte Chemie 2021, 133 (52) , 27276-27283. https://doi.org/10.1002/ange.202111993
    92. Aijie Cai, Wenhao Yan, Chao Wang, Wei Liu. Copper‐Catalyzed Difluoromethylation of Alkyl Iodides Enabled by Aryl Radical Activation of Carbon–Iodine Bonds. Angewandte Chemie International Edition 2021, 60 (52) , 27070-27077. https://doi.org/10.1002/anie.202111993
    93. Aijie Cai, Wenhao Yan, Xiaojun Zeng, Samson B. Zacate, Tzu-Hsuan Chao, Jeanette A. Krause, Mu-Jeng Cheng, Wei Liu. Copper-catalyzed carbo-difluoromethylation of alkenes via radical relay. Nature Communications 2021, 12 (1) https://doi.org/10.1038/s41467-021-23590-2
    94. Robert Britton, Veronique Gouverneur, Jin-Hong Lin, Michael Meanwell, Chuanfa Ni, Gabriele Pupo, Ji-Chang Xiao, Jinbo Hu. Contemporary synthetic strategies in organofluorine chemistry. Nature Reviews Methods Primers 2021, 1 (1) https://doi.org/10.1038/s43586-021-00042-1
    95. Luca Demonti, Nathalie Saffon‐Merceron, Nicolas Mézailles, Noel Nebra. Cross‐Coupling through Ag(I)/Ag(III) Redox Manifold. Chemistry – A European Journal 2021, 27 (62) , 15396-15405. https://doi.org/10.1002/chem.202102836
    96. Juanjuan Wu, Hongli Wu, Xinzhi Li, Xinyu Liu, Qian Zhao, Genping Huang, Chun Zhang. Copper‐Catalyzed Highly Selective Protoboration of CF 3 ‐Containing 1,3‐Dienes. Angewandte Chemie 2021, 133 (37) , 20539-20545. https://doi.org/10.1002/ange.202105896
    97. Juanjuan Wu, Hongli Wu, Xinzhi Li, Xinyu Liu, Qian Zhao, Genping Huang, Chun Zhang. Copper‐Catalyzed Highly Selective Protoboration of CF 3 ‐Containing 1,3‐Dienes. Angewandte Chemie International Edition 2021, 60 (37) , 20376-20382. https://doi.org/10.1002/anie.202105896
    98. He Liu, Qilong Shen. Well-defined organometallic Copper(III) complexes: Preparation, characterization and reactivity. Coordination Chemistry Reviews 2021, 442 , 213923. https://doi.org/10.1016/j.ccr.2021.213923
    99. Haiwen Xiao, Zhenzhen Zhang, Yewen Fang, Lin Zhu, Chaozhong Li. Radical trifluoromethylation. Chemical Society Reviews 2021, 50 (11) , 6308-6319. https://doi.org/10.1039/D1CS00200G
    100. Geunho Choi, Geun Seok Lee, Beomsoon Park, Dongwook Kim, Soon Hyeok Hong. Direct C(sp 3 )−H Trifluoromethylation of Unactivated Alkanes Enabled by Multifunctional Trifluoromethyl Copper Complexes. Angewandte Chemie 2021, 133 (10) , 5527-5534. https://doi.org/10.1002/ange.202012263
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    Cite this: J. Am. Chem. Soc. 2019, 141, 7, 3153–3159
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