Cytochrome P450 BM-3 from Bacillus megaterium was engineered for enantioselective epoxidation of simple terminal alkenes. Screening saturation mutagenesis libraries, in which mutations were introduced in the active site of an engineered P450, followed by recombination of beneficial mutations generated two P450 BM-3 variants that convert a range of terminal alkenes to either (R)- or (S)-epoxide (up to 83 % ee) with high catalytic turnovers (up to 1370) and high epoxidation selectivities (up to 95 %). A biocatalytic system using E. coli lysates containing P450 variants as the epoxidation catalysts and in vitro NADPH regeneration by the alcohol dehydrogenase from Thermoanaerobium brockii generates each of the epoxide enantiomers, without additional cofactor.
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FEMS Microbiol Lett
January 2025
Institute of Environmental Biotechnology, Graz University of Technology, Petersgasse 12/I, 8010, Graz, Austria.
Terminal olefins are important platform chemicals, drop-in compatible hydrocarbons and also play an important role as biocontrol agents of plant pathogens. Currently, 1-alkenes are derived from petroleum, although microbial biosynthetic routes are known. Jeotgalicoccus sp.
View Article and Find Full Text PDFArch Microbiol
January 2025
Department of Botany, CMS College Kottayam, Kottayam, Kerala, 686001, India.
Among all photosynthetic life forms, cyanobacteria exclusively possess a water-soluble, light-sensitive carotenoprotein complex known as orange carotenoid proteins (OCPs), crucial for their photoprotective mechanisms. These protein complexes exhibit both structural and functional modularity, with distinct C-terminal (CTD) and N-terminal domains (NTD) serving as light-responsive sensor and effector regions, respectively. The majority of cyanobacterial genomes contain genes for OCP homologs and related proteins, highlighting their essential role in survival of the organism over time.
View Article and Find Full Text PDFJ Am Chem Soc
January 2025
Key Laboratory of Applied Chemistry of Chongqing Municipality and Chongqing Key Laboratory of Soft-Matter Material Chemistry and Function Manufacturing, School of Chemistry and Chemical Engineering, Southwest University, Chongqing 400715, China.
Achieving catalytic asymmetric functionalization of methylenecyclopropanes (MCPs) by selective C-C bond cleavage is a notable challenge due to the intricate reaction partners involved. In this work, we report that chiral aldehyde/palladium combined catalysis enables the asymmetric functionalization of MCPs with NH-unprotected amino acid esters. This reaction proceeds through a regiospecific branched ring-opening mechanism, resulting in optically active α,α-disubstituted α-amino acid esters bearing nonconjugated terminal alkene units.
View Article and Find Full Text PDFChem Sci
December 2024
Department of Chemistry, The Scripps Research Institute 10550N. Torrey Pines Road, La Jolla CA 92037 USA
Catalytic alkene isomerization is a powerful synthetic strategy for preparing valuable internal alkenes from simple feedstocks. The utility of olefin isomerization hinges on the ability to control both positional and stereoisomerism to access a single product among numerous potential isomers. Within base-metal catalysis, relatively little is known about how to modulate reactivity and selectivity with group 6 metal-catalyzed isomerization.
View Article and Find Full Text PDFACS Catal
April 2024
Department of Chemistry, The Pennsylvania State University, University Park, Pennsylvania 16802, United States.
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