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A New Type of Stereoselectivity in Baeyer–Villiger Reactions: Access to E- and Z-Olefins

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http://pubman.mpdl.mpg.de/cone/persons/resource/persons59138

Zhang,  Zhi-Gang
Research Department Reetz, Max-Planck-Institut für Kohlenforschung, Max Planck Society;
Philipps-Universität Marburg, Fachbereich Chemie;

http://pubman.mpdl.mpg.de/cone/persons/resource/persons58934

Roiban,  Georghe-Doru
Research Department Reetz, Max-Planck-Institut für Kohlenforschung, Max Planck Society;
Philipps-Universität Marburg, Fachbereich Chemie;

http://pubman.mpdl.mpg.de/cone/persons/resource/persons58894

Polyak,  Iakov
Research Department Thiel, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

http://pubman.mpdl.mpg.de/cone/persons/resource/persons58919

Reetz,  Manfred T.
Research Department Reetz, Max-Planck-Institut für Kohlenforschung, Max Planck Society;
Philipps-Universität Marburg, Fachbereich Chemie;

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Supplementary Material (public)

adsc_201200759_sm_miscellaneous_information.pdf
(Supplementary material), 4MB

Citation

Zhang, Z.-G., Roiban, G.-D., Acevedo, J. P., Polyak, I., & Reetz, M. T. (2013). A New Type of Stereoselectivity in Baeyer–Villiger Reactions: Access to E- and Z-Olefins. Advanced Synthesis & Catalysis, 355(1), 99-106. doi:10.1002/adsc.201200759.


Cite as: http://hdl.handle.net/11858/00-001M-0000-0014-C920-4
Abstract
A new concept for accessing configurationally defined trisubstituted olefins has been developed. Starting from a common ketone precursor of the type 4-ethylidenecyclohexanone, Baeyer–Villiger monooxygenases are employed as catalysts in diastereoselective Baeyer–Villiger reactions leading to the corresponding E- or Z-configurated lactones. Wild-type cyclohexanone monooxygenase (CHMO) as catalyst delivers the E-isomers and a directed evolution mutant the opposite Z-isomers. Subsequent transition metal-catalyzed chemical transformations of a key product containing a vinyl bromide moiety provide a variety of different trisubstituted E- or Z-olefins. A model based on QM/MM sheds light on the origin of this unusual type of diastereoselectivity. In contrast to this biocatalytic approach, traditional Baeyer–Villiger reagents such as m-CPBA fail to show any selectivity, 1:1 mixtures of E- and Z-olefins being formed.