A new type of stereoselectivity in Baeyer-Villiger reactions: Access to E- and Z-olefins

Zhi Gang Zhang, Gheorghe Doru Roiban, Juan Pablo Acevedo, Iakov Polyak, Manfred T. Reetz

Research output: Contribution to journalArticlepeer-review

27 Scopus citations

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.

Original languageEnglish
Pages (from-to)99-106
Number of pages8
JournalAdvanced Synthesis and Catalysis
Volume355
Issue number1
DOIs
StatePublished - 14 Jan 2013

Keywords

  • Baeyer-Villiger oxidation
  • alkenes
  • diastereoselectivity
  • directed evolution
  • palladium

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