Table 1.
Primary homoallylic amines from Ti-mediated coupling.
 | ||||
|---|---|---|---|---|
| entry | aldehyde | allylic alcohol | yield (%) | product |
| 1 |
 8 |
 9 |
80 |
 10 |
| 2 |
 8 |
 11 |
76 |
 12 |
| 3 |
 13 |
 14 |
70 |
 15 |
| 4 |
 13 |
 16 |
83 |
 17 |
| 5 |
 18 |
 16 |
87 |
 19 |
| 6 |
 20 |
 11 |
72 |
 21 |
| 7 |
 22 |
 9 |
56 |
 23 |
| 8 |
 24 |
 9 |
53 |
 25 |
| 9 |
 26 |
 27 |
63 |
 28 |
Reaction conditions: RCHO (2 eq), LiHMDS (2 equiv), THF (−78 °C for aliphatic RCHO, −10 °C for aromatic aldehyde), then Ti(Oi-Pr)4 (2–3 equiv), RLi or RMgCl (4–6 eq), then Li-alkoxide of allylic alcohol (1 equiv) (−78 °C to rt). For specific examples, see Supporting Information. Note: products are racemic.