Vicinal C-H di-functionalization is an atypical strategy to rapidly add complexity to molecular scaffolds. The prevalence of hydroxyl groups in complex cores offers a unique handle for directing diversification of C-H bonds, and considering this, a strategy to achieve vicinal amino-functionalization of alcohols has been developed. This method is enabled by an imidate radical-chaperone that undergoes regioselective 1,5-hydrogen atom transfer to transpose a nitrogen-centered radical to the alcohol scaffold. Mechanistic investigations indicate a triiodide-mediated <i>in situ</i> desaturation, followed by polar amino-iodination to achieve vicinal di-functionalization. The utility of this strategy has been demonstrated through a series of post-synthetic transformations, giving rise to a diverse library of β,γ-di-functionalized alcohols.

Vicinal C-H di-functionalization via radical-polar crossover

2019 Spring National Meeting

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