Novel biocatalytic oxidative alkene cleavage

By serendipity we identified a novel biocatalytic reaction, which has never been used in organic chemistry before. Using molecular oxygen as oxidant, alkene cleavage can be performed to give the corresponding carbonyl compounds similar to ozonolysis. The scopes and limitations of this chemo-, regio- and stereoselective biocatalytic method for the oxidative alkene cleavage will be investigated. During the last years many efforts focus on the activation of molecular oxygen. Investigation of the reaction mechanism of the identified biocatalyst will give deeper insight into this matter and lead on the long range to the development of novel enzyme-mimetic organo- metal catalysts. Furthermore, compared to the current repertoire of alkene cleaving methods, the biocatalytic approach is environmentally compatible, sustainable, simple and cheap, since neither special equipment (e.g. ozonizer) nor additional (toxic) agents or salts (NaIO4 , OsO 4 , Cr-species) are needed, thus waste is avoided. The reaction can be performed in a simple round bottom flask at physiological conditions. During the course of the project the biocatalytic alkene cleavage will be optimized, the enzymes involved elucidated and the substrate spectrum, which can be transformed investigated. The catalysts chemo-, regio- and stereoselectivity, thus its ability to differentiate between various C=C double bonds within one molecule and to selectively oxidize the C=C bond in preference to other functional groups will be evaluated. Finally, preparative transformations will show the applicability of the method. The biocatalytic approach is not only of high interest because of its low cost and high sustainability, but because of its simplicity and especially due to its chemo-, regio-, and stereoselectivity. The project will lead to fundamental insights into the biological mechanism of oxygen-activation, which can be used for the development for novel bio-mimetic man-made catalysts for the selective use of the most innocuous oxidant (O2 ) for preparative organic chemistry.

By serendipity we identified a novel biocatalytic reaction, which has never been used in organic chemistry before. Using molecular oxygen as oxidant, alkene cleavage can be performed to give the corresponding carbonyl compounds similar to ozonolysis. The scopes and limitations of this chemo-, regio- and stereoselective biocatalytic method for the oxidative alkene cleavage will be investigated. During the last years many efforts focus on the activation of molecular oxygen. Investigation of the reaction mechanism of the identified biocatalyst will give deeper insight into this matter and lead on the long range to the development of novel enzyme-mimetic organo- metal catalysts. Furthermore, compared to the current repertoire of alkene cleaving methods, the biocatalytic approach is environmentally compatible, sustainable, simple and cheap, since neither special equipment (e.g. ozonizer) nor additional (toxic) agents or salts (NaIO4, OsO4, Cr-species) are needed, thus waste is avoided. The reaction can be performed in a simple round bottom flask at physiological conditions. During the course of the project the biocatalytic alkene cleavage will be optimized, the enzymes involved elucidated and the substrate spectrum, which can be transformed investigated. The catalysts chemo-, regio- and stereoselectivity, thus its ability to differentiate between various C=C double bonds within one molecule and to selectively oxidize the C=C bond in preference to other functional groups will be evaluated. Finally, preparative transformations will show the applicability of the method. The biocatalytic approach is not only of high interest because of its low cost and high sustainability, but because of its simplicity and especially due to its chemo-, regio-, and stereoselectivity. The project will lead to fundamental insights into the biological mechanism of oxygen-activation, which can be used for the development for novel bio-mimetic man-made catalysts for the selective use of the most innocuous oxidant (O2) for preparative organic chemistry.