Table 1.
Effect of Reaction Conditionsa
| ||||
|---|---|---|---|---|
| Entry | Substrate | Ligand | Yield (%) | ee 2 (%) |
|
| ||||
| 1 | 1a | 3a | 30b | -- |
| 2c | 1a | 3a | 48 | -- |
| 3c | 1a | 3c | 62 | 60 |
| 4c,d | 1a | 3c | 50 | 89 |
| 5c,d,e | 1a | 3c | 68 | 71 |
| 6 | 1b | 3a | 47 | -- |
| 7 | 1b | 3b | 78 | >95 |
| 8 | 1b | 3c | 64 | 94 |
| 9 | 1b | 3c | 47 | Nd |
| 10d | 1b | 3c | 78 | >95 |
| 11d,f | 1b | 3c | 75 | >95 |
| 12d,g | 1b | 3c | 48 | Nd |
| 13 | 1b | 3d | 84 | −89 |
| 14 | 1b | 3e | 81 | −84 |
| 15d | 1b | 3d | 78 | >−95 |
General conditions: 1 (0.18 mmol), 20 mol% Cu(OTf)2, 25 mol% 3, PhCF3 (0.1 M w/r to 1), 120 °C, 24 h, sealed tube, under Argon. MnO2 (85% by weight, <5 m particle size) was used.
30% product 2a along with 30% 1a and 33% of its corresponding aldehyde.
Ag2CO3 (1 equiv) was used instead of MnO2.
Reaction run in 1,2-dichloroethane (DCE) at 105 °C.
Reaction run with 2,6-di-tert-butyl-4-methylpyridine instead of K2CO3.
15 mol% Cu(OTf)2 and 19 mol% 3c were used.
10 mol% Cu(OTf)2 and 12.5 mol % 3c were used. Nd = not determined.