Screening conditions for regiodivergent tandem reactiona.
| ||||||
|---|---|---|---|---|---|---|
| Entry | [Pd] | L | Acid | x | Yieldb (%) | rrc |
| 1 | Pd(PPh3)4 | — | A1 | 20 | 75 | 52 : 48 |
| 2 | Pd(PPh3)4 | — | A2 | 20 | 65 | 63 : 37 |
| 3 | Pd(PPh3)4 | — | A3 | 20 | 60 | 54 : 46 |
| 4 | Pd(PPh3)4 | — | A1 | 50 | 90 | 75 : 25 |
| 5 | Pd(PPh3)4 | — | A1 | 100 | 91 | 94 : 6 |
| 6 | Pd(OAc)2 | PPh3 | A1 | 20 | 48 | 60 : 40 |
| 7 | [Pd(allyl)Cl]2 | PPh3 | A1 | 20 | 36 | 67 : 33 |
| 8 | Pd(allyl)Cp | PPh3 | A1 | 20 | 71 | 13 : 87 |
| 9 | Pd(allyl)Cp | PPh3 | A2 | 20 | 80 | 40 : 60 |
| 10 | Pd(allyl)Cp | PPh3 | A3 | 20 | 82 | 8 : 92 |
| 11 | Pd(allyl)Cp | PPh3 | A4 | 20 | 47 | 24 : 76 |
| 12 | Pd(allyl)Cp | PPh3 | A5 | 20 | Trace | — |
| 13 | Pd(allyl)Cp | PPh3 | A3 | 100 | 62 | 44 : 56 |
| 14d | Pd(PPh3)4 | — | A1 | 100 | 87 | 96 : 4 |
| 15d | Pd(allyl)Cp | PPh3 | A3 | 20 | 73 | 30 : 70 |
| 16e | Pd(PPh3)4 | — | A2 | 40 | 80 | 95 : 5 |
Unless noted otherwise, reactions were performed with 1,6-enyne 5b (0.1 mmol), imine 3a (0.05 mmol), [Pd] source (10 mol%), L (20 mol%), acid (x mol%) and 4 Å MS (20 mg) in degassed dry toluene (0.5 mL) at 70 °C for 12 h under Ar.
Isolated yield.
rr = 7a : 8a, determined by 1H-NMR analysis.
With 5c (0.1 mmol) instead of 5b.
With 1b (0.1 mmol) and 2a (0.1 mmol) instead of 5b at 80 °C.