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complexes as biohybrid catalysts. Acc Chem Res 52:945–954. https://doi.org/10.1021/acs.
accounts.8b00676
143. Oohora K, Meichin H, Zhao L, Wolf MW, Nakayama A, Hasegawa J, Lehnert N, Hayashi T
(2017) Catalytic cyclopropanation by myoglobin reconstituted with iron porphycene:
acceleration of catalysis due to rapid formation of the carbene species. J Am Chem Soc
139:17265–17268. https://doi.org/10.1021/jacs.7b10154
144. Key HM, Dydio P, Clark DS, Hartwig JF (2016) Abiological catalysis by artificial haem
proteins containing noble metals in place of iron. Nature 534:534–537. https://doi.org/10.
1038/nature17968
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409
57:4143–4148. https://doi.org/10.1002/anie.201708408
129. Prier CK, Zhang RK, Buller AR, Brinkmann-Chen S, Arnold FH (2017) Enantioselective,
intermolecular benzylic C–H amination catalysed by an engineered iron-haem enzyme. Nat
Chem 9:629–634. https://doi.org/10.1038/nchem.2783
130. Brandenberg OF, Miller DC, Markel U, Ouald Chaib A, Arnold FH (2019) Engineering
chemoselectivity in hemoprotein-catalyzed indole amidation. ACS Catal 9:8271–8275.
https://doi.org/10.1021/acscatal.9b02508
131. Farwell CC, Zhang RK, McIntosh JA, Hyster TK, Arnold FH (2015) Enantioselective
enzyme-catalyzed aziridination enabled by active-site evolution of a cytochrome P450. ACS
Cent Sci 1:89–93. https://doi.org/10.1021/acscentsci.5b00056
132. Roelfes G (2019) LmrR: a privileged scaffold for artificial metalloenzymes. Acc Chem Res
52:545–556. https://doi.org/10.1021/acs.accounts.9b00004
133. Bos J, Browne WR, Driessen AJM, Roelfes G (2015) Supramolecular assembly of artificial
metalloenzymes based on the dimeric protein lmrr as promiscuous scaffold. J Am Chem Soc
137:9796–9799. https://doi.org/10.1021/jacs.5b05790
134. Villarino L, Splan KE, Reddem E, Alonso-Cotchico L, Gutiérrez de Souza C, Lledós A,
Maréchal J-D, Thunnissen A-MWH, Roelfes G (2018) An artificial heme enzyme for
cyclopropanation reactions. Angew Chem Int Ed 57:7785–7789. https://doi.org/10.1002/
anie.201802946
135. Zhao J, Bachmann DG, Lenz M, Gillingham DG, Ward TR (2018) An artificial
metalloenzyme for carbene transfer based on a biotinylated dirhodium anchored within
streptavidin. Catal Sci Technol 8:2294–2298. https://doi.org/10.1039/C8CY00646F
136. Coelho PS, Brustad EM, Kannan A, Arnold FH (2013) Olefin cyclopropanation via carbene
transfer catalyzed by engineered cytochrome P450 enzymes. Science 339:307–310. https://
doi.org/10.1126/science.1231434
137. Vargas DA, Tinoco A, Tyagi V, Fasan R (2018) Myoglobin-catalyzed C–H functionalization of unprotected indoles. Angew Chem Int Ed 57:9911–9915. https://doi.org/10.1002/
anie.201804779
138. Tinoco A, Steck V, Tyagi V, Fasan R (2017) Highly diastereo- and enantioselective
synthesis of trifluoromethyl-substituted cyclopropanes via myoglobin-catalyzed transfer of
trifluoromethylcarbene. J Am Chem Soc 139:5293–5296. https://doi.org/10.1021/jacs.
7b00768
139. Tinoco A, Wei Y, Bacik J-P, Carminati DM, Moore EJ, Ando N, Zhang Y, Fasan R (2019)
Origin of high stereocontrol in olefin cyclopropanation catalyzed by an engineered carbene
transferase. ACS Catal 9:1514–1524. https://doi.org/10.1021/acscatal.8b04073
140. Reynolds EW, McHenry MW, Cannac F, Gober JG, Snow CD, Brustad EM (2016) An
evolved orthogonal enzyme/cofactor pair. J Am Chem Soc 138:12451–12458. https://doi.
org/10.1021/jacs.6b05847
141. Reynolds EW, Schwochert TD, McHenry MW, Watters JW, Brustad EM (2017) Orthogonal
expression of an artificial metalloenzyme for abiotic catalysis. ChemBioChem 18:2380–
2384. https://doi.org/10.1002/cbic.201700397
142. Oohora K, Onoda A, Hayashi T (2019) Hemoproteins reconstituted with artificial metal
complexes as biohybrid catalysts. Acc Chem Res 52:945–954. https://doi.org/10.1021/acs.
accounts.8b00676
143. Oohora K, Meichin H, Zhao L, Wolf MW, Nakayama A, Hasegawa J, Lehnert N, Hayashi T
(2017) Catalytic cyclopropanation by myoglobin reconstituted with iron porphycene:
acceleration of catalysis due to rapid formation of the carbene species. J Am Chem Soc
139:17265–17268. https://doi.org/10.1021/jacs.7b10154
144. Key HM, Dydio P, Clark DS, Hartwig JF (2016) Abiological catalysis by artificial haem
proteins containing noble metals in place of iron. Nature 534:534–537. https://doi.org/10.
1038/nature17968
Current Applications of Artificial Metalloenzymes …
409