Abstract
A computational study on the origin of the activating effect for Pd-catalyzed directed C–H activation by the concerted metalation-deprotonation (CMD) mechanism is conducted. DFT calculations indicate that strong acids can make Pd catalysts coordinate with directing groups (DGs) of the substrates more strongly and lower the C–H activation energy barrier. For the CMD mechanism, the electrophilicity of the Pd center and the basicity of the corresponding acid ligand for deprotonating the C–H bond are vital to the overall C–H activation energy barrier. Furthermore, this rule might disclose the role of some additives for C–H activation.
Highlights
Transition metal-catalyzed C–H activation to synthesize diverse organic molecules from simple hydrocarbon derivatives has emerged as a powerful tool for C–C and Cheteroatom bond formation and has received significant attention in recent years [1–7]
Yu and co-workers have established several strategies to overcome the low reactivity of C–H activation by weak coordination, such as using counter cation effect, auxiliaries and monoprotected amino acid ligands [31–35]
Using strong acid is a widely used strategy to promote C–H activation; for example, palladium(II)-catalyzed ortho-selective C–H chlorination/bromination has demonstrated that proper strong acids (TFA, TfOH) could promote the reactivity of ortho-selective C–H bond cleavage (Schemes 1 and 2) [25–30,38–40]
Summary
The Activating Effect of Strong Acid for Pd-Catalyzed Directed C–H Activation by Concerted Metalation-Deprotonation Mechanism. Transition metal-catalyzed C–H activation to synthesize diverse organic molecules from simple hydrocarbon derivatives has emerged as a powerful tool for C–C and Cheteroatom bond formation and has received significant attention in recent years [1–7]. They could widely promote C–H activation functionalization [22–24].
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