Methyl groups rank among the most abundant carbon fragments found in natural products and small-molecule pharmaceuticals. The late-stage and environmentally friendly installation of these groups onto biologically active molecules has attracted widespread attention in both industry and academia. In 2008, we published the first use of a methyl radical derived from a peroxide toward a directed transition-metal catalysed C-H methylation. In the past sixteen years, methyl-containing peroxides have proven themselves as robust reagents for introducing methyl groups onto organic molecules. In this review, our goal is to provide a thorough summary of the research advancements achieved in this field thus far.
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