Table 1. Intermolecular C–H Functionalization of N-Phenylpyrrolidine (2a) with Diazoacetone Using Hemoproteins and Variants Thereof^a.

entry	catalyst	yield (%)b	TONc	e.r.d (3a:4a)
1	Hemin	0	0	-
2	Mb (WT)	0	0	-
3	Mb (H64G, V68A)	0	0	-
4	P411-CHF	0	0	-
5	CYP119 (WT)	0	0	-
6	CYP119 (T213A)	0.4	35	nd
7	CYP119 (T213A, C317S)	2	170	69:31
8	CYP119 (T213A, V254A, C317S) CHI-g1	14	200	94:6
9	CYP119 (A209G, T213A, V254A, C317S) CHI-g2	23	3,100	99.5:0.5
10	CYP119 (F153G, A209G, T213A, V254A, C317S) CHI-DA	99	12,900	99.5:0.5
11e	CYP119 (F153G, A209G, T213A, V254A, C317S) CHI-DA	99	500	99.5:0.5
12f	CYP119 (F153G, A209G, T213A, V254A, C317S) CHI-DA	53	20,350	99.5:0.5

^aStandard reaction conditions: protein expressing C41(DE3) Escherichia coli cells, OD₆₀₀ = 40, 10 mM 2a, 20 mM diazoacetone (1a), in KPi buffer (50 mM, pH 7), room temperature, 16 h, in an anaerobic chamber.

^bAssay yields as determined by gas chromatography (GC) using calibration curves with the isolated product.

^cTON as calculated based on the protein concentration measured from cell lysate.

^dEnantiomeric ratio (e.r.) for 3a:4a as determined by chiral supercritical fluid chromatography (SFC).

^eUsing 20 μM purified protein and 10 mM Na₂S₂O₄.

^fOD₆₀₀ = 10. nd = not determined.