Mechanochemical catalytic oxidations in the solid state with in situ-generated modified IBX from 3,5-di-tert-butyl-2-iodobenzoic acid (DTB-IA)/Oxone?

Organic Chemistry Frontiers Pub Date: 2016-12-01 DOI: 10.1039/C6QO00588H

Abstract

IBX is an indispensable reagent in contemporary organic oxidation chemistry, despite its explosive and insoluble attributes. The latter drawbacks can be overcome if a more reactive modified version of IBX can be generated in situ catalytically. We show that the sterically-crowded reactive I(V) species can be generated catalytically from the precursor 3,5-di-tert-butyl-2-iodobenzoic acid (DTB-IA) in the presence of a terminal oxidant, i.e., Oxone. The highly reactive modified IBX, i.e., I(V) species, generated in situ from DTB-IA in the presence of Oxone under mechanochemical ball milling conditions, permits unprecedented oxidation of alcohols to carbonyl compounds, vicinal diols to oxidative cleavage products, and non-vicinal diols to lactones in the solid state. Indeed, the results constitute first demonstration of catalytic oxidations in the solid state using a modified o-iodobenzoic acid, an I(I) species.

Graphical abstract: Mechanochemical catalytic oxidations in the solid state with in situ-generated modified IBX from 3,5-di-tert-butyl-2-iodobenzoic acid (DTB-IA)/Oxone
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