Table 1. Optimization of the Reaction Conditions for the Reductive Cyclization.
| entry | solvent | T (°C) | time | base | yield (%) |
|---|---|---|---|---|---|
| 1 | THF | 70 | 5 h | CH(NMe)3 (5 equiv) | 0 |
| 2 | THF | 70 | 5 h | CH(NMe)2Ot-Bu (3 equiv) | 0 |
| 3 | DMF | rt | 18 h | TBAF (2 equiv) + HMPA (6 equiv) | 13 |
| 4 | DMF | 150 | 4 h | K2CO3 (2 equiv) + CuI (1 equiv) | 37 |
| 5 | DMF | 150 | 4 h | K2CO3 (2 equiv) | 36 |
| 6 | DMF | 150a | 15 min | K2CO3 (2 equiv) | 40 |
| 7 | DMF | 150a | 15 min | K2CO3 (4 equiv) | 44 |
| 8 | NMP | 150a | 15 min | K2CO3 (4 equiv) | 50 |
| 9 | NMP | 100a | 15 min | K2CO3 (4 equiv) | 29 |
| 10 | NMP | 200a | 15 min | K2CO3 (4 equiv) | 34 |
| 11 | NMP | 150a | 15 min | K2CO3 (10 equiv) | 55 |
| 12 | NMP | 150 | 1 h | K2CO3 (10 equiv) | 50 |
| 13 | NMPb | 150 | 1 h | K2CO3 (10 equiv) | 82 |
| 14c | NMPb | 150 | 1 h | K2CO3 (10 equiv) | 87 |
Use of microwaves.
Concentration = 0.01 M.
The reaction was carried out on a 1 mmol scale.
