Synthesis of Tetrasubstituted Nitroalkenes and Preliminary Studies of Their Enantioselective Organocatalytic Reduction
Abstract
:1. Introduction
2. Results and Discussion
2.1. Synthesis of Tetrasubstituted Nitroalkenes
2.2. Enantioselective Reduction of Tetrasubstituted Nitroalkenes (3)
2.3. Determination of the Absolute Configuration of Nitroalkanes (4)
3. Materials and Methods
3.1. General Procedure for the Synthesis of Tetrasubstituted Nitroalkenes (3)
3.2. General Procedure for the Enantioselective Synthesis of Nitroalkanes (4)
4. Conclusions
Supplementary Materials
Author Contributions
Funding
Institutional Review Board Statement
Informed Consent Statement
Data Availability Statement
Conflicts of Interest
Sample Availability
References
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Entry | R1 | R2 | T | Product | E/Z Ratio a | Yield b |
---|---|---|---|---|---|---|
1 | Me | Ph | RT | 2a | 80:20 | 52% |
2 | CF3 | Ph | RT | 2b | 75:25 | 79% |
3 | Me | tBu | 66 °C | 2c | 90:10 | 14% |
4 | iPr | Ph | 66 °C | 2d | 67:33 | 33% |
5 | Me | 4-BrPh | RT | 2e | 65:35 | 76% |
6 | Me | 4-MePh | 66 °C | 2f | 75:25 | 86% |
Entry | R1 | R2 | Acrylate | Nitroacrylate | Yield a | Isomers Ratio |
---|---|---|---|---|---|---|
1 | Me | Ph | 2a | 3a | 46% | 60/40 |
2 | CF3 | Ph | 2b | - | b | - |
3 | Me | tBu | 2c | 3c | --- c | - |
4 | iPr | Ph | 2d | 3d | 25% | 99/1 |
5 | Me | 4-BrPh | 2e | 3e | 47% | 62/38 |
6 | Me | 4-MePh | 2f | 3f | 48% | 57/43 |
Entry | T a | Nitroalkene | Nitroalkane | Catalyst | Yield d 4 | ee% Syn–ee% Anti e |
---|---|---|---|---|---|---|
1a | 60 °C | 3a–Z | 4a | A | trace | n.d. |
2b | 60 °C | 3a–E | 4a | A | 51% | 67-63 |
3c | 60 °C | 3a (E+Z) | 4a | A | 53% | 63–52 |
4c | 100 °C | 3a (E+Z) | 4a | A | 37% | 27–22 |
5c | 25 °C | 3a (E+Z) | 4a | A | 15% | n.d. |
6c | 60 °C | 3a (E+Z) | 4a | B | 69% | 33–32 |
7 | 60 °C | 3a (E+Z) | 4a | C | 19% | n.d. |
8 | 60 °C | 3a (E+Z) | 4a | D | 10% | n.d |
9 | 60 °C | 3d | 4d | A | 32% | 12–13 |
10 | 60 °C | 3e | 4e | A | 60% | 24–4 |
11 | 60 °C | 3f | 4f | A | 51% | 50–46 |
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González, P.C.; Rossi, S.; Sanz, M.; Vasile, F.; Benaglia, M. Synthesis of Tetrasubstituted Nitroalkenes and Preliminary Studies of Their Enantioselective Organocatalytic Reduction. Molecules 2023, 28, 3156. https://doi.org/10.3390/molecules28073156
González PC, Rossi S, Sanz M, Vasile F, Benaglia M. Synthesis of Tetrasubstituted Nitroalkenes and Preliminary Studies of Their Enantioselective Organocatalytic Reduction. Molecules. 2023; 28(7):3156. https://doi.org/10.3390/molecules28073156
Chicago/Turabian StyleGonzález, Patricia Camarero, Sergio Rossi, Miguel Sanz, Francesca Vasile, and Maurizio Benaglia. 2023. "Synthesis of Tetrasubstituted Nitroalkenes and Preliminary Studies of Their Enantioselective Organocatalytic Reduction" Molecules 28, no. 7: 3156. https://doi.org/10.3390/molecules28073156