Table 5.
Substrate Scope of hydroazidation and hydroamination

| Entry[a],[b] | 3 | Ar | 4, yield[c], ee[d] | 5, yield[c], ee[d] |
|---|---|---|---|---|
| 1 | 3a | Ph | 4a, 92, 90 | 5a, 89, 89 |
| 2 | 3b | 4-MeC6H4 | 4b, 89, 84 | 5b, 82, 80 |
| 3 | 3c | 4-SiMe3C6H4 | 4c, 67, 74 | 5c, 56, 73 |
| 4 | 3d | 4-PhC6H4 | 4d, 84, 84 | 5d, 49, 64 |
| 5 | 3e | 4-FC6H4 | 4e, 86, 86 | 5e, 75, 87 |
| 6 | 3f | 4-BrC6H4 | 4f, 88, 90 | 5f, 84, 92 |
| 7 | 3g | 4-CF3C6H4 | 4g, 41, 74 | 5g, 97, 92 |
| 8 | 3h | 3-MeC6H4 | 4h, 89, 85 | 5h, 63, 83 |
| 9 | 3i | 3-OMeC6H4 | 4i, 65, 84 | 5i, 82, 78 |
| 10 | 3j | 3-PhC6H4 | 4j, 92, 89 | 5j, 74, 72 |
| 11 | 3k | 3-BrC6H4 | 4k, 87, 88 | 5k, 77, 85 |
| 12 | 3l | 2-MeC6H4 | 4l, 81, 62 | 5l, 74, 80 |
| 13 | 3m | 3-thienyl | 4m, 86, 75 | 5m, 71, 77 |
Condition A: 0.1 mmol 3, 0.005 mmol A5·(AuCl)2, 0.015 mmol AgOTf, 0.3 mmol TMSN3, 0.2 mmol H2O, in 2.0 mL of THF:CHCl3 (3:1 v/v, 0.05M), 72 h at −10 °C. Condition B: 0.05 mmol 3, 0.0025 mmol A4·(AuCl)2, 0.006 mmol AgOTf, 0.15 mmol tert-butyl carbamate, in 1.0 mL of 1,4-dioxane (0.05M), 24 h at rt.
Absolute stereochemistry assigned by analogy to 4a and 5a.
Isolated yield.
Determined by chiral HPLC.