title: Myoglobin-Catalyzed Olefination of Aldehydes.
abstract: The olefination of aldehydes constitutes a most valuable and widely adopted strategy for constructing carbon-carbon double bonds in organic chemistry. While various synthetic methods have been made available for this purpose, no biocatalysts are known to mediate this transformation. Reported herein is that engineered myoglobin variants can catalyze the olefination of aldehydes in the presence of α-diazoesters with high catalytic efficiency (up to 4,900 turnovers) and excellent E diastereoselectivity (92-99.9 % de). This transformation could be applied to the olefination of a variety of substituted benzaldehydes and heteroaromatic aldehydes, also in combination with different alkyl α-diazoacetate reagents. This work provides a first example of biocatalytic aldehyde olefination and extends the spectrum of synthetically valuable chemical transformations accessible using metalloprotein-based catalysts.
authors.affiliation: Department of Chemistry, University of Rochester, 120 Trustee Road, Rochester, NY, 14627, USA.
authors.forename: Vikas
authors.identifier: http://orcid.org/0000-0002-8946-5773
authors.initials: V
authors.lastname: Tyagi
authors.affiliation: Department of Chemistry, University of Rochester, 120 Trustee Road, Rochester, NY, 14627, USA. fasan@chem.rochester.edu.
authors.forename: Rudi
authors.identifier: http://orcid.org/0000-0003-4636-9578
authors.initials: R
authors.lastname: Fasan
mesh_terms: D000447:Aldehydes / Q000737:chemistry*; D000475:Alkenes / Q000737:chemistry*; D002384:Catalysis; D009211:Myoglobin / Q000737:chemistry*
chemical_list: D000447:Aldehydes; D000475:Alkenes; D009211:Myoglobin
keywords: Wittig reactions; biocatalysis; carbenes; diazo compounds; protein engineering