Optimization of Lewis acids for the sequential reactiona.
| ||||
|---|---|---|---|---|
| Entry | Metal salt | Yieldbb (%) | 3aa : 4aac | ee of 4aac (%) |
| 1 | Ni(OTf)2 | 76 | 82 : 18 | 92 |
| 2 | Zn(OTf)2 | 54 | 6 : 94 | 91 |
| 3 | Mg(OTf)2 | 52 | 34 : 66 | 91 |
| 4 | Cu(OTf)2 | 49 | 1 : 99 | 93 |
| 5dd | Cu(OTf)2 | 70 | 1 : 99 | 93 |
| 6ee | Cu(OTf)2 | 70 | 1 : 99 | 93 |
Unless otherwise noted, all reactions were initially carried out with 1a (0.05 mmol), 2a (1.2 equiv.), L5-RaPr2 (10 mol%) and Ni(OTf)2 (10 mol%) in CH2Cl2 (0.2 M) at 35 °C for 16 h. Then, the metal salt (5 mol%) in CH2Cl2 (0.1 M) was added and stirred at 30 °C for 16 h under air.
Isolated yield of 4aa based on 1a.
Determined by HPLC on a chiral stationary phase.
4 Å MS (10 mg) in CHCl3 (0.05 M) was used for the second transformation for 3 h.
Isolated 3aa was treated with Cu(OTf)2 (5 mol%) and 4 Å MS (10 mg) in CHCl3 (0.05 M) at 30 °C for 4 h under N2.