Enantioselective Organocatalyzed Michael Addition of Isobutyraldehyde to Maleimides in Aqueous Media
Abstract
:1. Introduction
2. Results and Discussion
2.1. Asymmetric Michael Reaction of Maleimide and Aldehydes Using a Thiourea Catalyst
2.2. Reaction Mechanism Inferred through Expected Transition States
2.3. Pharmaceutical Applications Using Gram-Scale Asymmetric Reactions
3. Materials and Methods
3.1. Instruments and Reagents
3.2. Experimental Method
3.2.1. Synthesis of N-Mono-Thiourea Catalyst
3.2.2. Asymmetric Michael Reaction of Aldehyde and Maleimide Using a Chiral Thiourea Catalyst
3.2.3. Gram-Scale Asymmetric Michael Reaction of Aldehyde and Maleimide Using a Chiral Thiourea Catalyst
3.2.4. General Procedure of the Racemic Michael Addition
3.3. Results of Density Functional Theory Calculations and Discussion
4. Conclusions
Supplementary Materials
Author Contributions
Funding
Data Availability Statement
Acknowledgments
Conflicts of Interest
References
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Entry | Time (h) | Additive | Solvent | Yield (%) a | ee (%) b |
---|---|---|---|---|---|
1 | 24 | Trifluoro-acetic acid | CH2Cl2 | 78 | 98 |
2 | 24 | Acetic acid | CH2Cl2 | 83 | 94 |
3 | 24 | Salicylic acid | CH2Cl2 | 82 | 94 |
4 | 24 | Benzoic acid | Toluene | 78 | 99 |
5 | 24 | Benzoic acid | THF | 98 | 99 |
6 c | 0.67 | - | Water | 99 | 99 |
7 d | 6 | - | Water | 99 | 99 |
8 e | 12 | - | Water | 97 | 99 |
Entry | Ar | Time (h) | Yield (%) a | ee (%) b |
---|---|---|---|---|
1 | H | 10 | 98 | 99 |
2 | 4-MeC6H4 | 12 | 99 | 99 |
3 | 4-BrC6H4 | 12 | 98 | 99 |
4 | 4-NO2C6H4 | 12 | 97 | 99 |
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Shim, J.H.; Cheun, S.H.; Kim, H.S.; Ha, D.-C. Enantioselective Organocatalyzed Michael Addition of Isobutyraldehyde to Maleimides in Aqueous Media. Molecules 2022, 27, 2759. https://doi.org/10.3390/molecules27092759
Shim JH, Cheun SH, Kim HS, Ha D-C. Enantioselective Organocatalyzed Michael Addition of Isobutyraldehyde to Maleimides in Aqueous Media. Molecules. 2022; 27(9):2759. https://doi.org/10.3390/molecules27092759
Chicago/Turabian StyleShim, Jae Ho, Seok Hyun Cheun, Hyeon Soo Kim, and Deok-Chan Ha. 2022. "Enantioselective Organocatalyzed Michael Addition of Isobutyraldehyde to Maleimides in Aqueous Media" Molecules 27, no. 9: 2759. https://doi.org/10.3390/molecules27092759