ArticleACS catalysis2019
Origin of high stereocontrol in olefin cyclopropanation catalyzed by an engineered carbene transferase.
Article in ACS catalysis, 2019. The graph could read no effect estimate from its abstract, so it casts no vote on the map. Cited by 35 papers.
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Who cites it
35 citing papers in PubMed, 86 citations in OpenAlex.
- Direct Access to Iron Carbenes from Aldehyde, Ketone, and Formamide Feedstocks.Journal of the American Chemical Society · 2026Article
- PCA-Based Database Mining Enables the Discovery of Bacterial Carbene Transferases for Stereodivergent Cyclopropanation.Angewandte Chemie (International ed. in English) · 2026Article
- Computational design of generalist cyclopropanases with stereodivergent selectivity.Nature communications · 2026Article
- Highly Enantioselective Synthesis of Halogenated Cyclopropanes via Enzyme Catalyzed Carbene Transfer.ChemCatChem · 2025Article
- Automated Flow Synthesis of Artificial Heme Enzymes for Enantiodivergent Biocatalysis.Journal of the American Chemical Society · 2025Article
- Production of Phenyldiazene Derivatives Using the Biosynthetic Pathway of an Aromatic Diazo Group-Containing Natural Product from an Actinomycete.Chembiochem : a European journal of chemical biology · 2025Article
- Machine-Learning-Aided Engineering Hemoglobin as Carbene Transferase for Catalyzing Enantioselective Olefin Cyclopropanation.JACS Au · 2024Article
- Mechanistic investigation of sustainable heme-inspired biocatalytic synthesis of cyclopropanes for challenging substrates.Communications chemistry · 2024Article
- Radical-Mediated Regiodivergent C(Chem catalysis · 2024Article
- Hybrid Metal Catalysts as Valuable Tools in Organic Synthesis: An Overview of the Recent Advances in Asymmetric C─C Bond Formation Reactions.Molecules (Basel, Switzerland) · 2024Review
- Biocatalytic Strategy for the Highly Stereoselective Synthesis of Fluorinated Cyclopropanes.Angewandte Chemie (International ed. in English) · 2024Article
- Stereodivergent Synthesis of Pyridyl Cyclopropanes via Enzymatic Activation of Pyridotriazoles.Journal of the American Chemical Society · 2024Article
- Stereoselective Construction of β-, γ-, and δ-Lactam Rings via Enzymatic C-H Amidation.Nature catalysis · 2024Article
- Mechanistic manifold in a hemoprotein-catalyzed cyclopropanation reaction with diazoketone.Nature communications · 2023Article
- Dehaloperoxidase Catalyzed Stereoselective Synthesis of Cyclopropanol Esters.The Journal of organic chemistry · 2023Article
- Protoglobin-Catalyzed Formation of cis-Trifluoromethyl-Substituted Cyclopropanes by Carbene Transfer.Angewandte Chemie (International ed. in English) · 2023Article
- Stereoselective Construction of β-, γ-, and δ-Lactam Rings via Enzymatic C-H Amidation.Research square · 2023Article
- YfeX - A New Platform for Carbene Transferase Development with High Intrinsic Reactivity.Chemistry (Weinheim an der Bergstrasse, Germany) · 2022Article
- Biocatalytic Intramolecular C-H aminations via Engineered Heme Proteins: Full Reaction Pathways and Axial Ligand Effects.Chemistry (Weinheim an der Bergstrasse, Germany) · 2022Article
- Highly stereoselective and enantiodivergent synthesis of cyclopropylphosphonates with engineered carbene transferases.Chemical science · 2022Article
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Authors and funding
8 authors at 3 institutions in 1 country.
Funding
Abstract
Recent advances in metalloprotein engineering have led to the development of a myoglobin-based catalyst, Mb(H64V,V68A), capable of promoting the cyclopropanation of vinylarenes with high efficiency and high diastereo- and enantioselectivity. Whereas many enzymes evolved in nature often exhibit catalytic proficiency and exquisite stereoselectivity, how these features are achieved for a non-natural reaction has remained unclear. In this work, the structural determinants responsible for chiral induction and high stereocontrol in Mb(H64V,V68A)-catalyzed cyclopropanation were investigated via a combination of crystallographic, computational (DFT), and structure-activity analyses. Our results show the importance of steric complementarity and non-covalent interactions involving first-sphere active site residues, heme-carbene, and the olefin substrate, in dictating the stereochemical outcome of the cyclopropanation reaction. High stereocontrol is achieved through two major mechanisms. First, by enforcing a specific conformation of the heme-bound carbene within the active site. Second, by controlling the geometry of attack of the olefin on the carbene via steric occlusion, attractive van der Waals forces and protein-mediated π-π interactions with the olefin substrate. These insights could be leveraged to expand the substrate scope of the myoglobin-based cyclopropanation catalyst toward non-activated olefins and to increase its cyclopropanation activity in the presence of a bulky α-diazo-ester. This work sheds first light into the origin of enzyme-catalyzed enantioselective cyclopropanation, furnishing a mechanistic framework for both understanding the reactivity of current systems and guiding the future development of biological catalysts for this class of synthetically important, abiotic transformations.
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