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. Author manuscript; available in PMC: 2022 Jun 1.
Published in final edited form as: Curr Opin Biotechnol. 2020 Dec 25;69:43–51. doi: 10.1016/j.copbio.2020.12.005

Figure 2.

Figure 2

Hemoprotein-catalyzed carbene transfer reactions. (a) Selected carbene donors and acceptors in enzymatic carbene transfer reactions. All competent carbene donors are diazo compounds bearing an electron-withdrawing group adjacent to the diazo carbon [1923]. Carbene acceptors range from σ-bonds [19,25,26] to unsaturated π-systems [24●●,27●●,28]. Intramolecular carbene transfer reactions have also been developed to form ring structures [29,35]. (b) X-ray crystal structure of carbene-bound Rma cytochrome c (1.29 Å, PDB ID: 6CUN). Hydrophobic amino acid residues interacting with the carbene species are highlighted in yellow [30]. (c) Recent examples of enzymatic carbene transfer reactions that highlight the evolvability of hemoprotein scaffolds [24●●,27●●,28]. These include challenging transformations catalyzed by artificial metalloenzymes containing exogenously added Ir-porphyrin cofactors [38,39].