Heck Transformations of Biological Compounds Catalyzed by Phosphine-Free Palladium
Abstract
:1. Introduction
2. Results and Discussion
3. Materials and Methods
3.1. Reactants
3.2. General Procedures
3.2.1. Heck Reaction (Method A)
3.2.2. Heck-Type Reaction (Method B)
3.2.3. Heck-Type Reaction (Method C)
4. Conclusions
Supplementary Materials
Author Contributions
Funding
Conflicts of Interest
References
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Sample Availability: Samples of the compounds are not available from the authors. |
Entry | Catalyst | Base | DMF:H2O | T (°C) | Time (h) | PhI Conversion (%) | Yield (%) a | ||
---|---|---|---|---|---|---|---|---|---|
1E | 1Z | 1b | |||||||
1 | Pd(OAc)2 | K2CO3 | DMF | 100 | 3 | 100 | 81 | 16 | 3 |
2 | DMF | 100 | 1 | 95 | 78 | 15 | 2 | ||
3 | 4:1 | 100 | 3 | 100 | 84 | 14 | 2 | ||
4 | 4:1 | 100 | 2 | 100 | 85 | 15 | 0 | ||
5 | 4:1 | 100 | 1 | 100 | 85 | 13 | 1 | ||
6 | 2.5:2.5 | 100 | 2 | 100 | 79 | 21 | 0 | ||
7 | 2.5:2.5 | 100 | 1 | 93 | 69 | 23 | 1 | ||
9 | PdCl2(CH3CN)2 | DMF | 100 | 1 | 79 | 74 | 5 | 0 | |
10 | Pd(OAc)2 | 4:1 | 100 | 40 min | 74 | 65 | 7 | 2 | |
11 | 4:1 | 80 | 3 | 90 | 80 | 10 | 0 | ||
12 | 4:1 | 60 | 3 | 74 | 68 | 6 | 0 |
Entry | Catalyst | Base | DMF:H2O | T (°C) | Time (h) | PhI Conversion (%) | Yield (%) a | ||
---|---|---|---|---|---|---|---|---|---|
2E | 2Z | 2b | |||||||
1 | Pd(OAc)2 | K2CO3 | DMF | 80 | 3 | 71 | 36 | 30 | 5 |
2 | DMF | 100 | 3 | 96 | 47 | 42 | 7 | ||
4 | DMF | 100 | 1 | 77 | 40 | 31 | 6 | ||
5 | 2.5:2.5 | 100 | 1 | 41 | 24 | 14 | 3 | ||
3 | 4:1 | 100 | 3 | 61 | 35 | 22 | 4 | ||
6 | 4:1 | 100 | 1 | 15 | 11 | 4 | 0 | ||
7 | 4:1 | 80 | 3 | 37 | 28 | 9 | 0 |
Entry | Catalyst | Base | Modification | T (°C) | Time (h) | Eugenol Conversion (%) | Yield (%) a | ||
---|---|---|---|---|---|---|---|---|---|
1E | 1Z | 1b | |||||||
1 | Pd(OAc)2 | KOH | Air | 50 | 3 | 0 | 0 | 0 | 0 |
2 | Na2CO3 | Air | 50 | 3 | 0 | 0 | 0 | 0 | |
3 | K2CO3 | Air | 50 | 3 | 0 | 0 | 0 | 0 | |
3 | PdCl2cod | ˗ | Cu(OAc)2 | 120 | 4 | 55 | 21 | 21 | 7 |
4 | ˗ | 100 | 4 | 25 | 9 | 6 | 10 | ||
5 | ˗ | Cu(OAc)2.·H2O | 100 | 4 | 53 | 26 | 17 | 9 | |
6 | ˗ | Cu(OAc)2 | 120 | 4 | 57 | 26 | 25 | 6 | |
7 | Pd(OAc)2 | ˗ | 100 | 3 | 81 | 51 | 26 | 4 | |
8 | ˗ | 100 | 4 | 92 | 46 | 39 | 4 |
Entry | Catalyst | Base | Modification | T (°C) | Time (h) | Estragole Conversion (%) | Yield (%) a | ||
---|---|---|---|---|---|---|---|---|---|
2E | 2Z | 2b | |||||||
1 | Pd(OAc)2 | KOH | Air | 50 | 3 | 0 | 0 | 0 | 0 |
2 | Na2CO3 | Air | 50 | 3 | 0 | 0 | 0 | 0 | |
3 | PdCl2cod | ˗ | Cu(OAc)2 | 120 | 4 | 64 | 34 | 28 | 2 |
4 | ˗ | 100 | 4 | 34 | 22 | 12 | 0 | ||
5 | ˗ | Cu(OAc)2.·H2O | 100 | 4 | 59 | 32 | 24 | 3 | |
6 | Pd(OAc)2 | ˗ | Cu(OAc)2 | 100 | 2.5 | 89 | 46 | 39 | 4 |
7 | ˗ | 100 | 3 | 90 | 49 | 37 | 4 | ||
8 | ˗ | 100 | 4 | 92 | 47 | 41 | 4 |
Entry | Catalyst | Base | Modification | Time (h) | PhI Conversion (%) | Yield (%) b | ||||
---|---|---|---|---|---|---|---|---|---|---|
Bif. | 3 | 4 | 5 | 6 | ||||||
1 | PdCl2cod | NaOAc | ˗ | 6 | 68 | 15 | 13 | 29 | 7 | 2 |
2 | PdCl2cod | TBAB a | 6 | 91 | 5 | 28 | 52 | 3 | 3 | |
3 | PdCl2cod | DMF:H2O (1:1) | 6 | 93 | ˗ | 34 | 57 | ˗ | ˗ | |
4 | PdCl2cod | DMF:H2O (4:1) | 6 | 93 | 19 | 14 | 53 | ˗ | ˗ | |
5 | PdCl2cod | K2HPO4 | ˗ | 6 | 30 | ˗ | 11 | 19 | ˗ | ˗ |
6 | PdCl2cod | DMF:H2O (1:1) | 6 | 56 | 10 | 18 | 28 | ˗ | ˗ | |
7 | 24 | 96 | 2 | 8 | 72 | ˗ | 11 | |||
8 | PdCl2cod | DMF:H2O (1:4) | 6 | 68 | 10 | 13 | 40 | ˗ | ˗ | |
9 | PdCl2cod | Et3N | ˗ | 6 | 68 | 24 | 22 | 18 | ˗ | ˗ |
10 | DMF:H2O (1:1) | 6 | 67 | 5 | 26 | 36 | ˗ | ˗ |
Entry | Catalyst | Salt Cu2+ | T (°C) | Time (h) | Cinnamyl Alcohol Conversion (%) | Yield (%) b | ||
---|---|---|---|---|---|---|---|---|
3 | 4 | 7 | ||||||
1 | Pd(OAc)2 | Air | 100 | 4 | 0 | 0 | 0 | 0 |
2 | Cu(OAc)2 | 100 | 6 | 100 | 37 | 14 | 49 | |
3 | 100 | 4 | 100 | 40 | 16 | 44 | ||
4 | 50 | 1 | 90 | 18 | 6 | 63 | ||
5 | Pd2(dba)3 | 50 | 4 | 100 | 19 | 6 | 75 | |
6 | 50 | 1 | 100 | 20 | 6 | 74 | ||
7 a | 50 | 1 | 63 | 13 | 5 | 45 | ||
8 | 50 | 0.5 | 90 | 25 | 8 | 56 |
Entry | Catalyst | Base | Modification | Time (h) | PhI Conversion (%) | Yield (%) a | |
---|---|---|---|---|---|---|---|
8 | 9 | ||||||
1 | PdCl2cod | NaOAc | ˗ | 3 | 47 | 33 | 14 |
2 | DMF:H2O (4:1) | 3 | 95 | 66 | 29 | ||
3 | K2HPO4 | ˗ | 3 | 42 | 21 | 21 | |
4 | DMF:H2O (4:1) | 3 | 65 | 48 | 17 | ||
5 | Et3N | ˗ | 3 | 42 | 29 | 12 | |
6 | DMF:H2O (4:1) | 3 | 61 | 45 | 12 |
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Tarnowicz-Ligus, S.; Trzeciak, A.M. Heck Transformations of Biological Compounds Catalyzed by Phosphine-Free Palladium. Molecules 2018, 23, 2227. https://doi.org/10.3390/molecules23092227
Tarnowicz-Ligus S, Trzeciak AM. Heck Transformations of Biological Compounds Catalyzed by Phosphine-Free Palladium. Molecules. 2018; 23(9):2227. https://doi.org/10.3390/molecules23092227
Chicago/Turabian StyleTarnowicz-Ligus, Stanisława, and Anna M. Trzeciak. 2018. "Heck Transformations of Biological Compounds Catalyzed by Phosphine-Free Palladium" Molecules 23, no. 9: 2227. https://doi.org/10.3390/molecules23092227