1,3-dithiane-derived alkoxyamines as one-carbon radical precursors

A new method for the generation of C-2 centered radicals derived from 1,3-dithiane is presented. The radical precursors, 2-dialkylaminoxyl-l,3-dithianes, are readily prepared from 1,3-dithiane and stable nitroxides. Thermal reaction of 2-dialkylaminoxyl-1,3-dithianes with electron-deficient olefins affords carboaminoxylation products or oxidative addition products depending on the nitroxide used. The 2-dialkylaminoxyl-1,3-dithianes can also be used as initiators/regulators for the controlled living free radical polymerization of styrene.