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

研究成果: Article

22 引文 斯高帕斯(Scopus)

摘要

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.

原文English
頁(從 - 到)3153-3159
頁數7
期刊Journal of the American Chemical Society
141
發行號7
DOIs
出版狀態Published - 2019 二月 20

All Science Journal Classification (ASJC) codes

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

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