Practical and Efficient Large-Scale Preparation of Dimethyldioxirane

Abstract

An improved procedure for large-scale and also commercially viable preparation of dimethyldioxirane (DMDO), a common and widely used oxidation agent in organic synthesis, was developed using a conventional laboratory plant. All reaction parameters were optimized, and the stability of a freshly prepared solution of DMDO in acetone was monitored over an extended period of time to ensure long-term use after preparation, transport, and storage. This discontinuous approach, suitable for batch processing, is of interest basically to research laboratories but also to suppliers in the research and fine chemicals market.

Continued Progress towards Efficient Functionalization of Natural and Non‐natural Targets under Mild Conditions: Oxygenation by C−H Bond Activation with Dioxirane

“…[59] After applying ap rotecting group strategy to the groups of betulin prone to oxidation (e.g.,C 20 ÀC 30 alkenea nd C 3 and C 28 alcohols), [31] the authors obtained the derivative 33,w hich represents an excellent platform to examine the possibility of selectivity as af unction of innate CÀHo xidation. [59] Treatment of compound 33 with TFDO at 0 8Ca llowed the O-insertion to smoothly occur at the secondary C 16 ÀHb ond to provide the ketone 34 in 30 %yield as confirmed by X-ray crystallography (Scheme 12). [58] Scheme12.…”

“…To ensure long-term use after preparation, transport, and storage, they also reportedt hat aDDO solution in acetone remaineds table at ac oncentration of 40 mm for am inimum of 11 months. [16]…”

Lichtinduzierte Totalsynthese von 17‐Desoxyprovidencin

“…Auf dieser Stufe gelang die stereoselektive Epoxidierung des D-7,8-Olefins mit DMDO. [16] Wittig-Methylenierung der C16-Carbonylgruppe lieferte schließlich 17-Desoxyprovidencin (2). Eine NOE-Analyse bestätigte die korrekte Konfiguration am D-7,8-Epoxid,…”

“…Auf dieser Stufe gelang die stereoselektive Epoxidierung des D-7,8-Olefins mit DMDO. [16] Wittig-Methylenierung der C16-Carbonylgruppe lieferte schließlich 17-Desoxyprovidencin (2). Eine NOE-Analyse bestätigte die korrekte Konfiguration am D-7,8-Epoxid, [13a] woraus hervorgeht, dass trotz (oder wegen) der eingeschränkten konformativen Beweglichkeit des Makrocyclus der Angriff des DMDO an der gewünschten "Außenfassade" des Olefins stattgefunden hat.…”

Synthesis of 3a‐hydroxyhexahydropyrrolo[2,3‐B]Indole‐2‐carboxamide, an oxidation product of tryptophan present in natural products

“…DMDO is a highly effective oxygen‐transfer reagent that reacts with several substrate classes that include π‐bonds, heteroatom lone‐pairs, and even alkanes, which undergo selective C‐H insertion. DMDO and potassium peroxymonosulfate share a wide variety of substrates but DMDO has the following reactivity preference: heteroatom oxidation > alkene epoxidation > secondary alcohol oxidation > C‐H insertion …”