Cu (II)-Catalyzed Asymmetric Henry Reaction with a Novel C1-Symmetric Aminopinane-Derived Ligand
Abstract
:1. Introduction
2. Results and Discussion
Entry a | Copper Salt | Solvent | T (°C) | Time (h) | DIPEA (mol %) | Yield (%) b | e.e. (%) c |
---|---|---|---|---|---|---|---|
1 | CuCl2∙2H2O | THF | 4 | 20 | 100 | 90 | 53 |
2 | Cu(OAc)2∙H2O | THF | 4 | 20 | 100 | 52 | 52 |
3 | CuCl2∙2H2O | EtOH | 4 | 20 | 100 | 88 | 33 |
4 | Cu(OAc)2∙H2O | EtOH | 4 | 20 | 100 | 92 | 37 |
5 | Cu(OAc)2∙H2O | CH2Cl2 | 4 | 20 | 100 | 68 | 47 |
6 | Cu(OAc)2∙H2O | i-PrOH | 4 | 20 | 100 | 97 | 55 |
7 | Cu(OAc)2∙H2O | Et2O | 4 | 20 | 100 | 63 | 46 |
8 | Cu(OAc)2∙H2O | THF | −25 | 20 | 100 | <5 | n.d. d |
9 | Cu(OAc)2∙H2O | i-PrOH | −25 | 72 | 100 | 88 | 57 |
10 | Cu(OAc)2∙H2O | i-PrOH | 4 | 2 | 100 | 68 | 57 |
11 | Cu(OAc)2∙H2O | i-PrOH | 4 | 4 | 100 | 88 | 56 |
12 | Cu(OAc)2∙H2O | i-PrOH | 4 | 6 | 100 | 85 | 55 |
13 | Cu(OAc)2∙H2O | i-PrOH | 4 | 8 | 100 | 89 | 57 |
15 | Cu(OAc)2∙H2O | i-PrOH | 4 | 20 | 0 | 36 | 56 |
16 | Cu(OAc)2∙H2O | i-PrOH | 4 | 20 | 5 | 88 | 57 |
17 | Cu(OAc)2∙H2O | i-PrOH | 4 | 20 | 10 | 98 | 56 |
Entry a | R | Aldehyde | Product | Yield (%) b | e.e. (%) c |
---|---|---|---|---|---|
1 | n-Bu | 5a | 6a | 91 | 57 |
2 | i-Bu | 5b | 6b | 89 | 49 |
3 | t-Bu | 5c | 6c | 88 | 67 |
4 | i-Pr | 5d | 6d | 83 | 60 |
5 | n-nonyl | 5e | 6e | 75 | 55 |
6 | n-undecyl | 5f | 6f | 82 | 53 |
7 | trans-2-decenyl | 5g | 6g | 65 | 47 |
8 d | phenyl | 5h | 6h | 80 | 38 |
9 e | phenyl | 5h | 6h | 63 | 45 |
10 f | phenyl | 5h | 6h | 10 | 76 |
Entry a | R | Product | Yield (%) b | syn/anti (%) c | ee (%) d |
---|---|---|---|---|---|
1 | i-Bu | 7a | 93 | 58/42 | 54/38 |
2 | i-Pr | 7b | 94 | 81:19 | 66/34 |
3. Experimental Section
3.1. Preparation of Ligands
3.1.1. Synthesis of (E)-1-(1-Methyl-1H-imidazol-2-yl)-N-((1S,2S,3S,5R)-2,6,6-trimethylbicyclo[3.1.1]heptan-3-yl)methanimine (3)
3.1.2. Synthesis of (1S,2S,3S,5R)-2,6,6-Trimethyl-N-((1-methyl-1H-imidazol-2-yl)methyl)-bicyclo[3.1.1]heptan-3-amine (4)
3.2. General Procedure for the Enantioselective Henry Reaction
3.2.1. R-(−)-1-Nitro-2-hexanol (6a)
3.2.2. R-(+)-4-Methyl-1-nitropentan-2-ol (6b)
3.2.3. R-(−)-3,3-Dimethyl-1-nitrobutan-2-ol (6c)
3.2.4. R-(−)-3-Methyl-1-nitrobutan-2-ol (6d)
3.2.5. R-(−)-1-Nitroundecan-2-ol (6e)
3.2.6. R-(−)-1-Nitrotridecan-2-ol (6f)
3.2.7. R-(−)-(E)-1-Nitroundec-3-en-2-ol (6g)
3.2.8. (R)-(−)-1-Phenyl-2-nitroethanol (6h)
3.2.9. (2R,3R)-5-Methyl-2-nitrohexane-3-ol (7a)
3.2.10. (3R, 4R)-2-methyl-4-nitropentan-3-ol (7b)
4. Conclusions
Acknowledgments
Author Contributions
Conflicts of Interest
References
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- Sample Availability: Sample of the ligand 4 is available from the authors.
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Filippova, L.; Stenstrøm, Y.; Hansen, T.V. Cu (II)-Catalyzed Asymmetric Henry Reaction with a Novel C1-Symmetric Aminopinane-Derived Ligand. Molecules 2015, 20, 6224-6236. https://doi.org/10.3390/molecules20046224
Filippova L, Stenstrøm Y, Hansen TV. Cu (II)-Catalyzed Asymmetric Henry Reaction with a Novel C1-Symmetric Aminopinane-Derived Ligand. Molecules. 2015; 20(4):6224-6236. https://doi.org/10.3390/molecules20046224
Chicago/Turabian StyleFilippova, Liudmila, Yngve Stenstrøm, and Trond Vidar Hansen. 2015. "Cu (II)-Catalyzed Asymmetric Henry Reaction with a Novel C1-Symmetric Aminopinane-Derived Ligand" Molecules 20, no. 4: 6224-6236. https://doi.org/10.3390/molecules20046224