Non‐Directed Functionalization of Distal C (sp 3 ) H Bonds

What is it about?

This chapter describes the activation and functionalization of Csp3H bonds in remote positions from functional groups. The selective activation of these bonds over others can be achieved by exploiting and/or tuning intrinsic parameters in the substrates (bond dissociation energies, steric hindrance) or in the catalysts used for the activation process (metal‐carbon bond properties, steric hindrance of the ligand). In the first part of the chapter, an explanation of the different factors influencing the selectivity of CH bond activation is given. A selection of powerful functionalization methods, both traditional and modern, each with examples of recent applications, is then provided, together with selectivity considerations. Finally, the last part of the chapter describes the strategy of so‐called polarity reversal, a general method to tune the properties of CH bonds in a substrate so to alter the innate reactivity of CH bonds, and therefore the selectivity of functionalization.

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