352-59-0Relevant academic research and scientific papers
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
supporting information, p. 3153 - 3159 (2019/03/06)
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.
Free Radical Substitution. Part 37. The Effect of Solvent on the Atomic Chlorination of 1-Substituted Butanes and Related Compounds
Potter, Alan,Tedder, John M.
, p. 1689 - 1692 (2007/10/02)
Experimental results reported in this paper show that the relative selectivity of atomic chlorination of 1-substituted butanes and related compounds is greatly influenced by the phase and by solvents.Solvents can be divided into three classes: (a) inert, (b) solvents which decrease the selectivity, and (c) solvents which increase the selectivity.The second group solvate the transition state and the third group solvate the chlorine atoms.
