Oxidation reaction alkenes

Computational studies of alkene oxidation reactions by metal-oxo compounds, 38, 131 Computational studies on the mechanism of orotidine monophosphate decarboxylase,... 

The reaction mechanisms of these transition metal mediated oxidations have been the subject of several computational studies, especially in the case of osmium tetraoxide [7-10], where the controversy about the mechanism of the oxidation reaction with olefins could not be solved experimentally [11-20]. Based on the early proposal of Sharpless [12], that metallaoxetanes should be involved in alkene oxidation reactions of metal-oxo compounds like Cr02Cl2, 0s04 and Mn04" the question arose whether the reaction proceeds via a concerted [3+2] route as originally proposed by Criegee [11] or via a stepwise [2+2] process with a metallaoxetane intermediate [12] (Figure 2). 

Computational studies of alkene oxidation reactions by metal-oxo compounds,... 

Takacs, J.M. and Jiang, X.-t. (2003) The Wacker reaction and related alkene oxidation reactions. Curr. Org. Chem., 7, 369. 

The activation of oxygen in oxygen transfer reactions is usually mediated by a suitable transition metal catalyst which has to be sufficiently stable under the reaction conditions needed. But also non-metal catalysts for homogeneous oxidations have recently been of broad interest and several of them have been compiled in a recent review.2 Other examples for well known alkene oxidation reactions are the ozonolysis, hydroboration reactions or all biological processes, where oxygen is activated and transferred to the substrate. Examples for these reactions might be cytochrome P450 or other oxotransferases. Of these reactions, this contribution will focus on transition-metal mediated epoxidation and dihydroxylation. 

Frei and co-workers have also used TRIR techniques toexamine mechanisms of alkene oxidation reactions in zeolites S. Vasenkov, H. Frei, J. Phys. Chem. B1998,702,8177. 

Andrews MA, Chang TCT, Cheng CWF, Emge TJ, Kelly KP, Koetzle TF (1984) Synthesis, characterization, and equilibria of palladium(ii) nitrile, alkene, and heterometallacy-clopentane complexes involved in metal nitro catalyzed alkene oxidation reactions. J Am Chem Soc 106 5913-5920... 

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