Modification of the Swern Oxidation: Use of Stoichiometric Amounts of an Easily Separable, Recyclable, and Odorless Sulfoxide That Can Be Polymer-Bound

Publisher Website
Google Scholar
Abstract
Readily available 6-(methylsulfinyl)hexanoic acid (1) is employed as a substitute for DMSO in Swern oxidation reactions using oxalyl chloride to smoothly convert primary or secondary alcohols to corresponding aldehydes or ketones in high yield. The resulting 6-(methylthio)hexanoic acid (2) is easily separable by aqueous extraction or by filtration through silica gel and can be reoxidized to 1 with sodium metaperiodate in 97% yield. Low temperature (−60 °C) 13C NMR spectrometry is used to examine the intermediates of this Swern process. The results indicate that any residual unoxidized alcohol is generated during Pummerer elimination of the alkoxysulfonium intermediate and can be minimized by extended exposure to triethylamine at −40 °C. Reaction of the potassium salt of 1 with cross-linked chloromethyl polystyrene affords a polymer-bound reagent 12 that quantitatively oxidizes borneol to camphor when used in two-fold excess.