Work

Chemoselective Oxidation of Equatorial Alcohols with N-Ligated λ3-Iodanes

Year: 2019

Type: article

Abstract: The site-selective and chemoselective functionalization of alcohols in complex polyols remains a formidable synthetic challenge. Whereas significant advancements have been made in selective derivatization at the oxygen center, chemoselective oxidation to the corresponding carbonyls is less developed. In cyclic systems, whereas the selective oxidation of axial alcohols is well known, a complementary equatorial selective process has not yet been reported. Herein we report the utility of nitrogen-ligated (bis)cationic λ 3 -iodanes ( N -HVIs) for alcohol oxidation and their unprecedented levels of selectivity for the oxidation of equatorial over axial alcohols. The conditions are mild, and the simple pyridine-ligated reagent ( Py-HVI ) is readily synthesized from commercial PhI(OAc) 2 and can be either isolated or generated in situ. Conformational selectivity is demonstrated in both flexible 1,2-substituted cyclohexanols and rigid polyol scaffolds, providing chemists with a novel tool for chemoselective oxidation.

Source: Organic Letters

DOI: 10.1021/acs.orglett.9b02018

Authors: Myriam Mikhael, Sophia A. Adler, Sarah E. Wengryniuk

Institution: Temple University

Language: English

Topic: Oxidative Organic Chemistry Reactions

Subfield: Organic Chemistry

Field: Chemistry

Domain: Physical Sciences

Open Access status: green

Funders: National Science Foundation, University of Pennsylvania, National Institute of General Medical Sciences, Division of Chemistry

Awards: G3221074797, Simplified Approaches to Medium-Sized Heterocycles for the Synthesis of Bioactive Small Molecules