945491-50-9Relevant academic research and scientific papers
Reversible Concerted Metalation-Deprotonation C-H Bond Activation by [Cp*RhCl2]2
Vanderweide, Andrew I.,Brennessel, William W.,Jones, William D.
supporting information, p. 12960 - 12965 (2019/10/11)
The reversibility of the concerted metalation-deprotonation exchange of eight para-substituted phenylpyridines is examined with the parent Cp*RhCl(κ-C,N-NC5H4-C6H4). Equilibrium constants are determined, and the free energies are used to extract the most important parameters that control the thermodynamics. Keq values are found to correlate best with heterolytic C-H bond strengths but in a way that is not obvious considering the electrophilic nature of these activations.
Cross-Coupling of α-Carbonyl Sulfoxonium Ylides with C?H Bonds
Barday, Manuel,Janot, Christopher,Halcovitch, Nathan R.,Muir, James,A?ssa, Christophe
supporting information, p. 13117 - 13121 (2017/10/11)
The functionalization of carbon–hydrogen bonds in non-nucleophilic substrates using α-carbonyl sulfoxonium ylides has not been so far investigated, despite the potential safety advantages that such reagents would provide over either diazo compounds or their in situ precursors. Described herein are the cross-coupling reactions of sulfoxonium ylides with C(sp2)?H bonds of arenes and heteroarenes in the presence of a rhodium catalyst. The reaction proceeds by a succession of C?H activation, migratory insertion of the ylide into the carbon–metal bond, and protodemetalation, the last step being turnover-limiting. The method is applied to the synthesis of benz[c]acridines when allied to an iridium-catalyzed dehydrative cyclization.
