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

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.

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adsc_201200759_sm_miscellaneous_information.pdf (Supplementary material), 4MB
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adsc_201200759_sm_miscellaneous_information.pdf
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Supporting Information
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2012
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Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim
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 Creators:
Zhang, Zhi-Gang1, 2, Author           
Roiban, Georghe-Doru1, 2, Author           
Acevedo, Juan Pablo3, Author
Polyak, Iakov4, Author           
Reetz, Manfred T.1, 2, Author           
Affiliations:
1Research Department Reetz, Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_1445588              
2Philipps-Universität Marburg, Fachbereich Chemie, Hans-Meerwein-Strasse, 35032 Marburg, Germany, ou_persistent22              
3Facultad de Medicina y Facultad de Ingeniera y Ciencias Aplicadas, Universidad de los Andes, ou_persistent22              
4Research Department Thiel, Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_1445590              

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Free keywords: alkenes; Baeyer–Villiger oxidation; diastereoselectivity; directed evolution; palladium
 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.

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Language(s): eng - English
 Dates: 2012-10-162012-08-242013-01-072013-01-14
 Publication Status: Published in print
 Pages: 8
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1002/adsc.201200759
 Degree: -

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Title: Advanced Synthesis & Catalysis
  Abbreviation : Adv. Synth. Catal.
Source Genre: Journal
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Publ. Info: Weinheim, Fed. Rep. of Germany : Wiley-VCH Verlag GmbH
Pages: 8 Volume / Issue: 355 (1) Sequence Number: - Start / End Page: 99 - 106 Identifier: ISSN: 1615-4150
CoNE: https://pure.mpg.de/cone/journals/resource/958634688013