Oxymetallation. Part 17. t-Butyl peroxymercuriation and subsequent demercuriation of phenylcyclopropane

Abstract

Phenylcyclopropane reacts with mercury(II) trifluoroacetate and two equivalents of t-butyl hydroperoxide in dichloromethane to give a mixture of PhCH(OOBu^t)CH₂CH₂HgO₂CCF₃(47%) and PhCH(O₂CCF₃)CH₂CH₂HgO₂CCF₃(36%). Reduction with alkaline sodium borohydride converts this mixture into one of PhCH(OOBu^t)Et and PhCH (OH)Et, from which the pure peroxide (19% overall) has been isolated by silica chromatography. Brominolysis of the corresponding mixture of organomercury bromides followed by silica chromatography has afforded PhCH(OOBu^t)CH₂CH₂Br (29% overall).