Dimethyldioxirane (DMD)

Abstract

(A) Oxidation of Epoxy Alcohols: Willard and co-workers have reported conversion of epoxy alcohols into their corresponding epoxy ketones in high yields by selective oxidation using DMD without affecting the configuration at the epoxy functionality.4 (Chemical Equation Presented) (B) Oxidation of Iodoarenes: 2-Iodoylphenol ethers were prepared by DMD oxidation of corresponding 2-iodophenol ether and isolated as chemically stable, microcrystalline products.8 (Chemical Equation Presented) (C) Oxidation of N-Substituted Indole and Oxyindole: Suarez-Castillo et al. have developed a general and practical protocol for synthesizing 3-hydroxyoxindoles starting from indole and oxyindole derivatives. The methodology has been exploited to synthesize various medicinally important natural products. 9 (Chemical Equation Presented) (D) Hydroxylation Reaction: DMD selectively affords 2-hydroxy-3,4-dienoates by oxidizing zirconiumallenyl enolates10a and oxidation of benzylidene derivatives with DMD in methanol leads to the formation of either 1,2-diol or monomethylated 1,2-diol governed by the adjacent crowding.10b (Chemical Equation Presented) (E) Epoxidation Reactions: Dondoni and co-workers have reported a multi-gram epoxidation of 3,4,6-tri-O-benzyl-D-glucal and D-galactal with DMD resulting in the formation of the corresponding 1,2-anhydrosugars in 99% yield and 100% stereoselectivity.11a Recently, epoxidation of allene has been reported to give isolable SDEs (spiro-fused diepoxides).11b (Chemical Equation Presented) (F) Nef Reaction: DMD selectively converts nitroalkanes into carbonyl compounds by oxidation at the nitronoate center (obtained by treatment of NO2 with base).12a Makosza et al. have reported oxidation of nitrobenzylic carbanions proceeding at the carbanion center to give hydroxyl compounds and at the nitronoate group to produce quinomethanes. The reaction course is governed by the substituent at the carbanion center and the reaction conditions: solvents and counteranion. In some cases, a peculiar reaction leading to methylation of the carbanion is observed.12b,c (Chemical Equation Presented) © Georg Thieme Verlag Stuttgart.