α-Functionalization of Ketones via a Nitrogen Directed Oxidative Umpolung

Abstract

Reversing the polarity in molecules is a versatile tool for expanding the boundaries of structural space. Despite a manifold of different umpolung methods available today, overcoming the inherent reactivity still remains a constant challenge in organic chemistry. The oxidative α-functionalization of ketones by external nucleophiles constitute such an example. Herein, we present a hypervalent F-iodane mediated umpolung of pyridyl ketones triggered by Lewis base Lewis acid non-covalent interactions. A wide variety of external nucleophiles are introduced with high regioselectivity applying this substratedirecting concept.<br>

Cyclic Haloiodanes: Syntheses, Applications and Fundamental Studies

“…Gulder and Kiefl recently reported the nitrogen‐directed α‐functionalization of ketones using fluoroiodane 2a ( Scheme 36). [58] This enables the addition of nucleophiles at the α‐position of the ketone, which is traditionally nucleophilic as well. A wide range of nucleophiles and substituents are tolerated.…”