Computational Studies of Carboxylate-Assisted C–H Activation and Functionalization at Group 8–10 Transition Metal Centers

2017/05/22 by David L. Davies, Stuart A. Macgregor, Claire L. McMullin · 2 citations
Chemistry · #Catalytic C–H Functionalization Methods #Asymmetric Hydrogenation and Catalysis #Synthesis and Catalytic Reactions

paper · doi:10.1021/acs.chemrev.6b00839

openalex publication_date 2017/05/22 · openalex created_date 2025/10/10 · openalex updated_date 2026/07/30

Abstract

Computational studies on carboxylate-assisted C–H activation and functionalization at group 8–10 transition metal centers are reviewed. This Review is organized by metal and will cover work published from late 2009 until mid-2016. A brief overview of computational work prior to 2010 is also provided, and this outlines the understanding of carboxylate-assisted C–H activation in terms of the “ambiphilic metal–ligand assistance” (AMLA) and “concerted metalation deprotonation” (CMD) concepts. Computational studies are then surveyed in terms of the nature of the C–H bond being activated (C(sp 2 )–H or C(sp 3 )–H), the nature of the process involved (intramolecular with a directing group or intermolecular), and the context (stoichiometric C–H activation or within a variety of catalytic processes). This Review aims to emphasize the connection between computation and experiment and to highlight the contribution of computational chemistry to our understanding of catalytic C–H functionalization based on carboxylate-assisted C–H activation. Some opportunities where the interplay between computation and experiment may contribute further to the areas of catalytic C–H functionalization and applied computational chemistry are identified.

Citations

• Proton-Abstraction Mechanism in the Palladium-Catalyzed Intramolecular Arylation: Substituent Effects
• Semiempirical GGA‐type density functional constructed with a long‐range dispersion correction
• A consistent and accurateab initioparametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu
• Effect of the damping function in dispersion corrected density functional theory
• Evolution of C–H Bond Functionalization from Methane to Methodology
• Carboxylate-Assisted Transition-Metal-Catalyzed C−H Bond Functionalizations: Mechanism and Scope
• Mild metal-catalyzed C–H activation: examples and concepts

Cited by

• Direct Observation of the Microscopic Reverse of the Ubiquitous Concerted Metalation Deprotonation Step in C–H Bond Activation Catalysis
• Concerted metalation deprotonation [wikipedia]