Table 1. Optimization Studies.
entrya | ligand | additive | 3 (%)b | 4 (%)b | 5 (%)b | 6 (%)b |
---|---|---|---|---|---|---|
1 | PPh3 | <5 | 30 | 30 | 25 | |
2 | PCy3 | 15 | 42 | 23 | 14 | |
3 | IMes | 24 | 36 | 19 | <5 | |
4 | IPr | 22 | <5 | 5 | <5 | |
5 | Xantphos | 30 | <5 | 30 | <5 | |
6 | DPEphos | 50 | 24 | 25 | <5 | |
7 | dppf | 35 | 14 | 12 | <5 | |
8 | dppe | 11 | <5 | <5 | <5 | |
9 | dppp | 40 | 18 | 20 | <5 | |
10 | dcpe | 25 | 16 | 12 | <5 | |
11 | dcpe*c | 60 | <5 | <5 | 15 | |
12 | dcpe | P(O)Ph3 | 72 | <5 | <5 | 8 |
13 | dcped | 35 | <5 | <5 | <5 | |
14 | <5 | 30 | 22 | <5 | ||
15 | P(O)Ph3 | <5 | 8 | 6 | <5 | |
16e | dcpe | P(O)Ph3 | 60 | <5 | <5 | 10 |
17f | dcpe | P(O)Ph3 | 23 | 28 | 30 | 15 |
Reactions run on a 0.3 mmol scale. Diastereomeric ratio of 3 >95:5 in all cases.
Determined by 1H NMR analysis using 1,3,5-trimethoxybenzene as the internal standard.
dcpe* = dcpe:dcpe(O):dcpe(O)2 in a 3:1:3 ratio.
12 mol %.
NaOtBu used instead of LiOtBu.
NaOMe used instead of LiOtBu.