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

Matthew Paeth, Sam B. Tyndall, Liang Yu Chen, Jia Cheng Hong, William P. Carson, Xingwu Liu, Xiaodong Sun, Jinjia Liu, Kundi Yang, Elizabeth M. Hale, David L. Tierney, Bin Liu, Zhi Cao, Mu Jeng Cheng, William A. Goddard, Wei Liu

Research output: Contribution to journalArticle

11 Citations (Scopus)

Abstract

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.

Original languageEnglish
Pages (from-to)3153-3159
Number of pages7
JournalJournal of the American Chemical Society
Volume141
Issue number7
DOIs
Publication statusPublished - 2019 Feb 20

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Copper
Carbon
Kinetics
Discrete Fourier transforms
X-Ray Diffraction
Nuclear magnetic resonance spectroscopy
Mass spectrometry
Mass Spectrometry
Magnetic Resonance Spectroscopy
Diffraction
X rays
Crystals
Temperature

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Paeth, M., Tyndall, S. B., Chen, L. Y., Hong, J. C., Carson, W. P., Liu, X., ... Liu, W. (2019). Csp3-Csp3 Bond-Forming Reductive Elimination from Well-Defined Copper(III) Complexes. Journal of the American Chemical Society, 141(7), 3153-3159. https://doi.org/10.1021/jacs.8b12632
Paeth, Matthew ; Tyndall, Sam B. ; Chen, Liang Yu ; Hong, Jia Cheng ; Carson, William P. ; Liu, Xingwu ; Sun, Xiaodong ; Liu, Jinjia ; Yang, Kundi ; Hale, Elizabeth M. ; Tierney, David L. ; Liu, Bin ; Cao, Zhi ; Cheng, Mu Jeng ; Goddard, William A. ; Liu, Wei. / Csp3-Csp3 Bond-Forming Reductive Elimination from Well-Defined Copper(III) Complexes. In: Journal of the American Chemical Society. 2019 ; Vol. 141, No. 7. pp. 3153-3159.
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abstract = "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.",
author = "Matthew Paeth and Tyndall, {Sam B.} and Chen, {Liang Yu} and Hong, {Jia Cheng} and Carson, {William P.} and Xingwu Liu and Xiaodong Sun and Jinjia Liu and Kundi Yang and Hale, {Elizabeth M.} and Tierney, {David L.} and Bin Liu and Zhi Cao and Cheng, {Mu Jeng} and Goddard, {William A.} and Wei Liu",
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Paeth, M, Tyndall, SB, Chen, LY, Hong, JC, Carson, WP, Liu, X, Sun, X, Liu, J, Yang, K, Hale, EM, Tierney, DL, Liu, B, Cao, Z, Cheng, MJ, Goddard, WA & Liu, W 2019, 'Csp3-Csp3 Bond-Forming Reductive Elimination from Well-Defined Copper(III) Complexes', Journal of the American Chemical Society, vol. 141, no. 7, pp. 3153-3159. https://doi.org/10.1021/jacs.8b12632

Csp3-Csp3 Bond-Forming Reductive Elimination from Well-Defined Copper(III) Complexes. / Paeth, Matthew; Tyndall, Sam B.; Chen, Liang Yu; Hong, Jia Cheng; Carson, William P.; Liu, Xingwu; Sun, Xiaodong; Liu, Jinjia; Yang, Kundi; Hale, Elizabeth M.; Tierney, David L.; Liu, Bin; Cao, Zhi; Cheng, Mu Jeng; Goddard, William A.; Liu, Wei.

In: Journal of the American Chemical Society, Vol. 141, No. 7, 20.02.2019, p. 3153-3159.

Research output: Contribution to journalArticle

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T1 - Csp3-Csp3 Bond-Forming Reductive Elimination from Well-Defined Copper(III) Complexes

AU - Paeth, Matthew

AU - Tyndall, Sam B.

AU - Chen, Liang Yu

AU - Hong, Jia Cheng

AU - Carson, William P.

AU - Liu, Xingwu

AU - Sun, Xiaodong

AU - Liu, Jinjia

AU - Yang, Kundi

AU - Hale, Elizabeth M.

AU - Tierney, David L.

AU - Liu, Bin

AU - Cao, Zhi

AU - Cheng, Mu Jeng

AU - Goddard, William A.

AU - Liu, Wei

PY - 2019/2/20

Y1 - 2019/2/20

N2 - 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.

AB - 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.

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