Oxygen atom transfer amines

For practical reasons the two-electron oxidations of such prototypical substrates as alkenes, sulfides, amines and phosphines with peroxynitrous acid have been smdied since this type of oxygen atom transfer reaction is similar to the corresponding oxidations with peroxyformic acid, where both experimental and computational data are available The oxidative reactions (equations 3-6) of these key substrates can... 

VII. OXYGEN ATOM TRANSFER FROM SELECTED HYDROPEROXIDES A. The Oxidation of Amines... 

Dimethyldioxirane (52) and other methyldioxiranes are easily generated peroxides which have proved to be very useful oxygen atom transfer agents alkenes, sulfides and amines can all be oxidized and dimethyldioxirane is reduced to acetone. ... 

Jeong J, Lee D, Chang S (2015) Copper-catalyzed oxygen atom transfer of iV-oxides leading to a facile deoxygenation procedure applicable to both heterocyclic and amine IV-oxides. Chem Common 51 7035-7038. doi 10.1039/c5cc01739d... 

Enby 6 is an example of a stereospecific elimination reaction of an alkyl halide in which the transition state requires die proton and bromide ion that are lost to be in an anti orientation with respect to each odier. The diastereomeric threo- and e/ytAra-l-bromo-1,2-diphenyl-propanes undergo )3-elimination to produce stereoisomeric products. Enby 7 is an example of a pyrolytic elimination requiring a syn orientation of die proton that is removed and the nitrogen atom of the amine oxide group. The elimination proceeds through a cyclic transition state in which the proton is transferred to die oxygen of die amine oxide group. 

From the first transition state (TSl, Fig. 1), the reaction path leads to the tetrahedral intermediate 1 (INTI). In the latter, the proton transfer from methanol to the tertiary amine function is completed (from 1.183 to 1.059 A), and the negative charge at the former carbonyl oxygen atom reaches its maximum. This charge is compensated by a further shortening of the bifurcated hydrogen bonds to 2.040 A (-0.103 A) and 1.765 A (-0.096 A) (Fig. 1). The thiourea moiety thus forms an oxyanion hole similar to the amide groups of the serine protease backbone [41]. 

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