The chemoselective functionalization of complex molecules remains an outstanding synthetic challenge. Selective alcohol oxidation enables functionalization at a particular α-carbon in polyol scaffolds through oxidation of a desired hydroxyl group to the corresponding carbonyl. Advancement in this area is scarce and the conventional methods usually require the use of toxic transition metals, which poses environmental and economic concerns. Moreover, in cyclic systems, the selective oxidation of axial alcohols can be readily achieved via Cr(VII) oxidants, however the complimentary equatorial selectivity remains elusive. Herein, an unprecedented level of selectivity in the oxidation of equatorial over axial alcohols is demonstrated via the utilization of a simple pyridine-ligated I(III)-reagent, or Py-HVI. The Py-HVI is a member of an emerging class of (bis)cationic nitrogen-ligated I(III) reagents known as N-HVIs, and is readily synthesized from commercially available PhI(OAc)2 and pyridine upon activation with a silyl triflate. The Py-HVI can be pre-synthesized or we report a novel in situ protocol allowing the oxidation of alcohols directly from PhI(OAc)2 under mild conditions. The method is shown to be quite general and displays exceptional levels of conformational selectivity for equatorial alcohols in both flexible and rigid systems. In conclusion, a novel tool for chemoselective oxidation of alcohols enabled by N-HVI reagents is established opening new doors for chemists for future synthetic applications.

Chemoselective oxidation of equatorial alcohols with nitrogen-ligated λ3 iodanes

Macromolecular Chemistry: The Second Century

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ACS Spring 2020 National Meeting & Expo

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.