Table 2. Substrate scope of the combined photoredox/enzyme catalysis a .
Entry | Substrate | Photocat. & reducing agent | Biocat. | Product | Yield [e.e.] (%) b |
1 | Na3Ir(sppy)3(1 mol%) + AscH2 (0.2 M) | — | >95 c | ||
2 | 1b | Na3Ir(sppy)3 (1 mol %) + AscH2 (0.2 M) | MAO-N-9 (180 mg) | >95 [98] | |
3 | Na3Ir(sppy)3 (1 mol %) + AscH2 (0.2 M) | — | >95 c | ||
4 | 1c | Na3Ir(sppy)3 (1 mol %) + AscH2 (0.2 M) | MAO-N-9 (180 mg) | >95 [8] | |
5 | Na3Ir(sppy)3 (1 mol %) + AscH2 (0.2 M) | — | >95 c | ||
6 | 1d | Na3Ir(sppy)3 (1 mol %) + AscH2 (0.2 M) | MAO-N-9 (180 mg) | >95 [>99] | |
7 | Ru(bpy)3Cl2(1 mol %) + AscH2 (20 mM) + MPAA-PEG (10 eq.) + MPA-PEG (100 eq.) | — | >95 d | ||
8 | 1e | Ru(bpy)3Cl2(1 mol %) + AscH2 (20 mM) + MPAA-PEG (10 eq.) + MPA-PEG (100 eq.) | MAO-N-9 (180 mg) | >95 [35] e |
aReaction conditions: 1 (10 mM), E. coli whole cells (MAO-N-9) (180 mg, wet weight), photocatalyst (1 mol%) and reducing agent as specified in each case, in 1.0 mL phosphate buffer solution (pH 8.0) at ambient temperature with 405 or 450 nm LED (3 W) irradiation on a shaking agitator (at 200 rpm, only used for reactions with biocatalyst) for 30 h under air.
bYields were determined by 1H NMR analysis, enantiomeric excess was determined by chiral phase GC or HPLC.
c10 h.
d3 h.
e20 h.