Table 3. Selected results for the optimization of the performance of [η6-(arene)Ru(Biot-p-L)Cl]⊂(strept)avidin as an artificial metalloenzyme for the transfer hydrogenation of acetophenone derivatives 2a-c by using formate·boric acid as a reducing agent in 0.15 M Mops buffer.
Entry | Ligand | η6-arene | Protein | Substrate | Temperature, °C | Time, h | Conversion, % | ee, % |
---|---|---|---|---|---|---|---|---|
1 | Biot-p-L | p-cymene | Sav | 2a | 45 | 40 | 40 | 66 (R) |
2 | Biot-p-L | Benzene | Sav | 2a | 45 | 40 | 30 | 63 (S) |
3 | Biot-p-L | p-cymene | Sav | 2a | 55 | 64 | 82 | 68 (R) |
4 | Biot-p-L | p-cymene | P64G Sav | 2a | 55 | 64 | 90 | 85 (R) |
5 | Biot-p-L | p-cymene | P64G Sav | 2b | 55 | 64 | 97 | 89 (R) |
6 | Biot-p-L | p-cymene | P64G Sav | 2c | 55 | 64 | 92 | 94 (R) |
7 | Biot-p-L | p-cymene | P64G S112 G Sav | 2a | 55 | 40 | Quantitative | 67 (R) |
8 | Biot-p-L | p-cymene | P64G S112 G Sav | 2b | 55 | 40 | Quantitative | 88 (R) |
9 | Biot-p-L | p-cymene | P64G S112 G Sav | 2c | 55 | 40 | Quantitative | 90 (R) |
10 | Biot-p-L | Benzene | P64G Sav | 2c | 45 | 64 | 34 | 57 (S) |
11 | Biot-p-L | Benzene | P64G Sav | 2c | 55 | 64 | 44 | 44 (S) |
All catalytic runs were carried out at pHinitial = 6.25 by using the mixed buffer HCO2Na (0.5 M) + B(OH)3 (0.47 M) combined with Mops (0.15 M) with a Ru/substrate 2 a-c/formate ratio of 1:100:4,500. Conversions and enantioselectivity were determined by HPLC on Chiralcel OB-H.