Upon converting a carbonyl to its ketyl radical, the carbon is rendered nucleophilic, opening a new manifold of polarity-reversed couplings. Currently, the use of these ketyls are limited by the need for strong, stoichiometric reductants that reduce other sensitive functional groups. In this study, mild ketyl reduction is made possible by first converting aldehydes to their corresponding α-acetoxy iodides. In this form, the C-I bond is weaker (58 kcal/mol) allowing for an I<b><sup>.</sup></b> abstraction by a Mn catalyst. We have demonstrated that this ketyl radical can couple with imines for a cross-selective aza-pinacol reaction.

Mild ketyl radical generation via atom transfer catalysis

2019 Spring National Meeting

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