Csp^3-Csp^3 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 III, Wei Liu
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 Csp^3–Csp^3 bonds. We report herein a general method for the synthesis of a series of [alkyl-Cu^(III)-(CF_3)_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 Csp^3–CF^3 bonds proceeds through a concerted transition state, with a ΔH⧧ = 20 kcal/mol barrier.
Group Members
Paeth, M., Tyndall, S. B., Chen, L., Hong, J., Carson, W. P., Liu, X., Sun, X., Liu, J., Yang, K., Hale, E. M., Tierney, D. L., Liu, B., Cao, Z., Cheng, M., III, W. A. G., & Liu, W. (2019). Csp^3-Csp^3 Bond-Forming Reductive Elimination from Well-Defined Copper(III) Complexes. *J. Am. Chem. Soc.*, *141*(7), 3153-3159. https://doi.org/10.1021/jacs.8b12632