Table 1.
Evaluation of reaction conditions for the Ir-catalyzed allylation.[a]
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Entry | Additive | Yield [%][b] | dr[c] | ee [%][d] |
1 | - | 95 | 2.0:1 | n.d. |
2 | LiCl | >99 | 1:1.1 | n.d. |
3 | ZnCl2 | 72 | 16:1 | n.d. |
4 | CuI | 97 | 5.7:1 | n.d. |
5 | CuCl | 58 | 10:1 | n.d. |
6 | CuBr | >99 (>99) | 14:1 | 92 |
7 | CuCN | 34 | 2.5:1 | n.d. |
8 | CuOAc | 52 | 1.5:1 | n.d. |
9 | CuSCN | 94 | 2.3:1 | n.d. |
10[e] | CuBr | 42 | 2.7:1 | n.d. |
11[f] | CuBr | >99 | 14:1 | 93 |
12[g] | CuBr | >99 | 12:1 | 95 |
13 | CuBr2 | 0 | - | n.d. |
The molar ratio of 1a/2a/3/LHMDS/additive = 2/1/0.02/2/2. The absolute configuration of 4aa was assigned by analogy.
Combined yield of two diastereoisomers. Determined by 1H NMR analysis with mesitylene as internal standard. The yield in parentheses is an isolated yield of two diastereoisomers.
Determined by 1H NMR analysis of crude reaction mixtures.
Determined by chiral SFC analysis of the major isomer.
KHMDS was used as the base instead of LHMDS.
1 equiv of CuBr was used.
0.5 equiv of CuBr was used.
n.d. = not determined.