Primary amines dimethyldioxirane

Aliphatic and aromatic primary amines are rapidly and efficiently oxidized to nitro compounds by dimethyldioxirane.111 Dimethyldioxirane is prepared by reaction of OXONE (DuPont trademark)-2KHS05-KHS04-K2S04 with buffered aqueous acetone.112... 

Tertiary alkyl primary amines can be oxidized to nitro compounds in excellent yields with KMn04.39S This type of nitro compound is not easily prepared in other ways. All classes of primary amine (including primary, secondary, and tertiary alkyl as well as aryl) are oxidized to nitro compounds in high yields with dimethyldioxirane.399 Other reagents that oxidize various types of primary amines to nitro compounds are dry ozone,4,111 various peracids,401 including peracetic and peroxytrifluoroacetic acids, f-butyl hydroperoxide in the presence of certain molybdenum and vanadium compounds,402 F7-H20-MeCN,41123 and sodium perborate.403... 

Tertiary amine oxides can be converted into TV-hydroxy secondary amines provided that one of the TV-substituents can be selectively eliminated. This procedure has been applied to the synthesis of secondary A-hydroxy-a-amino acids 34 from the corresponding secondary a-amino acids using the /V-cyanoethyl group for transient protection of the secondary amine (Scheme 10) J40l More recently, direct oxidation with 2,2-dimethyldioxirane of a primary amine has been described for H-L-Val-OMe (82% yield) and H-L-Phe-OMe (54% yield))13 The reaction proceeds smoothly without epimerization, but no experimental details have been reported. 

AMI and PM3 calculations reveal that epoxidations by DMDO and TFDO involve peroxide-bond cr at a very early stage and that TFDO is the most reactive dioxirane as the CF3 group in it stabilizes this cr level. In accord with previous calculations a spiro transition state is predicted. Furthermore, allene is predicted to be less reactive than alkenes toward epoxidation by DMDO.192 DFT calculations on the oxidation of primary amines by dimethyldioxirane predict a late transition state with a barrier of 17.7 kcal mol-1 which is drastically lowered by hydrogen bonding to the O—O bond to just 1.3 kcal mol-1 in protic solvents.193... 

Dimethyldioxirane oxidizes primary amines to nitro compounds either preformed349 in acetone or in situ.350... 

Dimethyldioxirane, together with acetone, is removed from the reaction vessel by distillation. The yellow 0.1-0.2 M solution can be used as an oxidizing agent, e.g. for the epoxidation of olefins [19], for the oxidation of enolates to a-hydroxycarbonyl compounds and for the oxidation of primary amines into nitro compounds ... 

Oxidation of primary amines RNH2 with dimethyldioxirane (235), generated from acetone and oxone , 2KHS05-KHS04-K2S02, affords the corresponding nitro compounds Fluorine reacts with wet acetonitrile to produce an oxidizing... 

Polymer-supported permthenate has also been used in two convergent pathways for the synthesis of isoxazoUdines with each route employing different starting materials in order to create the maximum structural diversity [73]. In the first route secondary hydroxylamines, readily prepared from amines by in situ treatment with dimethyldioxirane, were oxidized directly to nitrones using polymer-supported permthenate (PSP). Alternatively, primary alcohols were used as the... 

Primary, secondary and tertiary aliphatic amines are efficiently converted to nitro compounds in 80-90 % yield with dimethyldioxirane, a reagent prepared from the reaction of oxone (2KHSO5-KHSO4-K2SO4) with buffered acetone. Dimethyldioxirane (DMDO) has been used for the synthesis of 1,3,5,7-tetranitroadamantane (71) from the corresponding tetraamine as the tetrahydrochloride salt (70) and is an improvement over the initial synthesis using permanganate anion (Table 1.7). ° Oxone is able to directly convert some aromatic amines into nitro compounds. 

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