Table 1 Screening of two metal complexes catalyzing the dehydrative allylation of 1a and 2a
From: Stereodivergent dehydrative allylation of β-keto esters using a Ru/Pd synergistic catalyst
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Entry | M1XL1(mol%) | RuL2 (mol%) | Time (h) | Yield (%) | (R,S) | (S,S) | (S,R) | (R,R) |
1 | PdL1R(OTf) (2) | RuL2S (2) | 6 | >99 | 99.7 | 0.1 | 0.2 | <0.1 |
2 | PdL1R(OTf) (1) | RuL2S (1) | 12 | >99 | 99.5 | 0.4 | 0.1 | <0.1 |
3 | PdL1R(OTf) (0.25) | RuL2S (0.25) | 24 | >99 | 98.8 | 1.0 | 0.2 | <0.1 |
4 | PdL1R(OTf) (2) | RuL2R (2) | 6 | 37 | <0.1 | 0.1 | 14.8 | 85.0 |
5 | PdL1R(OTf) (2) | RuL2R(2) | 24 | >99 | <0.1 | 0.2 | 14.8 | 84.8 |
6 | PdL1R(OTf) (4) | RuL2R(2) | 24 | >99 | <0.1 | 0.1 | 21.4 | 78.5 |
7 | PdL1R(OTf) (1) | RuL2R(2) | 72 | >99 | <0.1 | 0.2 | 7.1 | 92.7 |
8a | PdL1R(OTf) (1) | RuL2R(2) | 72 | 98 | <0.1 | 0.1 | 3.9 | 96.0 |
9a | PdL3R(OTf) (1) | RuL2R(2) | 72 | 36 | <0.1 | 0.2 | 8.9 | 90.9 |
10a | PdL4R(OTf) (1) | RuL2R(2) | 72 | <5 | n.d. | n.d. | n.d. | n.d. |
11a | PdL5R(OTf) (1) | RuL2R(2) | 72 | 91 | <0.1 | 0.1 | 3.7 | 96.1 |
12 | PdL1R(OTs) (1) | RuL2R(2) | 72 | <5 | n.d. | n.d. | n.d. | n.d. |
13 | PdL1R(BF4) (1) | RuL2R(2) | 72 | 38 | <0.1 | 0.1 | 12.0 | 87.9 |
14a | NiL1R(OTf) (1) | RuL2R(2) | 72 | <5 | n.d. | n.d. | n.d. | n.d. |
15a | CuL6R(OTf) (1) | RuL2R(2) | 72 | <5 | n.d. | n.d. | n.d. | n.d. |
16a | CuL2R(OTf) (1) | RuL2R(2) | 72 | <5 | n.d. | n.d. | n.d. | n.d. |
17 | TfOH (2) | RuL2R (2) | 12 | <5 | n.d. | n.d. | n.d. | n.d. |
18 | p-TsOH (2) | RuL2R (2) | 12 | <5 | n.d. | n.d. | n.d. | n.d. |
19 | PdL1R(OTf) (2) | (0) | 12 | 0 | n.d. | n.d. | n.d. | n.d. |
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