Table 2. Screening bisphosphine ligands for asymmetric hydrogenation of 2-phenylbenzo[b]thiophene 1,1-dioxide 1a a .
| |||
Entry | Ligand | Conv. b [%] | ee c [%] |
1 | ZhaoPhos L1 | >99 | >99 |
2 | L2 | >99 | >99 |
3 | L3 | 73 | 56 |
4 | L4 | NR | NA |
5 d | ZhaoPhos L1 | 81 | 96 |
6 d | L2 | 95 | 98 |
aUnless otherwise mentioned, all reactions were carried out with a [Rh(NBD)2]BF4/ligand/substrate 1a (0.1 mmol) ratio of 1 : 1.1 : 100 in 1.0 mL CF3CH2OH under 50 atm H2 at 70 °C for 40 h, and the catalyst was pre-complexed in CH2Cl2 (0.1 mL for each reaction vial).
bDetermined by 1H NMR analysis.
cThe ee value was determined by HPLC on a chiral phase.
dCatalyst loading is 0.5 mol%, 12 h. NR = no reaction, NA = not available.