Optimization of reaction conditionsa.
(b) Additive screening | |||||
---|---|---|---|---|---|
Entry | Additives | C b | eec (%) | s d | |
(R)-1a-1 | (S)-3a-1 | ||||
1 | BQ | 18 | 17 | 78 | 10 |
2 | 2-Chloro BQ | 39 | 50 | 77 | 13 |
3 | 2,5-dichloro BQ | 35 | 40 | 75 | 10 |
Reaction conditions:rac-1a-1 (0.1 mmol), ethyl acrylate 2a (0.6 equiv.), Pd(OAc)2 (10 mol%), ligand (30 mol%), Ag2CO3 (2.0 equiv.), 2-Cl-BQ (0.3 equiv.), 1,2-DCE (1.0 mL), N2, 75 °C, 3 days.
Calculated conversion, C = eeSM/(eeSM + eePR).
Determined by chiral HPLC analysis.
Selectivity (s) = ln[(1 − C)(1 − eeSM)]/ln[(1 − C)(1 + eeSM)].
2a (2.0 equiv.) used.