a) Self‐assembly of CuII‐Phen/LmrR artificial metalloenzyme in E. coli cells and catalyzed enantioselective Friedel–Crafts alkylation reaction. b) Results of catalysis of the enantioselective Friedel–Crafts alkylation reaction of 1 with 2 a by CuII‐Phen/LmrR and CuII‐Phen/SUMO in cell‐free extract and whole cells. In vitro catalysis: 120 μM LmrR, 90 μM CuII‐Phen, 1 mM 1 and 2 a in 20 mM MOPS, 150 mM NaCl, pH 7 at 4 °C for 30 min; in vivo catalysis: E. coli C43(DE3) cells over‐expressing LmrR (from a 0.5 mL overnight culture; OD600nm=4), 90 μM CuII‐Phen, 1 mM 1 and 2 a in catalysis buffer at 4 °C. Values are given as the average of independent duplicate experiments, each performed in duplo. Errors margins are standard deviations. c) Experimental design of the catalysis experiments with whole cells and supernatant. Values of copper content as determined by ICP‐OES are given in solid boxes. In dashed boxes are the samples that were used for catalytic reaction I: the Friedel–Crafts alkylation of 2 b with 1, and catalytic reaction II: the Friedel–Crafts alkylation of 2 a with 1.