Amine-Catalyzed Decarboxylative Aldol Reaction of β-Ketocarboxylic Acids with Trifluoropyruvates
Abstract
:1. Introduction
2. Results and Discussion
3. Materials and Methods
3.1. General
3.2. Materials
3.3. Synthesis of α,α-dialkyl-β-ketocarboxylic Acid 1c
3.4. General Procedure for the Decarboxylative Aldol Reaction
3.5. General Procedure of the Enantioselective Decarboxylative Aldol Reaction
Supplementary Materials
Author Contributions
Funding
Conflicts of Interest
References
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Entry | Catalyst | Solvent | Time (h) | Yield (%) 2 | dr 3 | |
---|---|---|---|---|---|---|
2a | 3a | |||||
1 | none | toluene | 4 | <1 | 20 | 66:33 |
2 | PhCH2CH2NH2 | toluene | 4 | 2 | 10 | 55:45 |
3 | (PhCH2)2NH | toluene | 4 | 58 | 10 | 92:8 |
4 | | toluene | 4 | 19 | 12 | 88:12 |
5 | pyridine | toluene | 4 | 6 | 4 | 68:32 |
6 | DMAP | toluene | 4 | 39 | 9 | 82:18 |
7 | Et3N | toluene | 4 | 96 | 1 | 86:14 |
8 | (quinuclidine) | toluene | 2 | 98 | 1 | 93:7 |
9 | (DABCO) | toluene | 2 | 94 | 3 | 92:8 |
10 4 | DABCO | toluene | 8 | 92 | 3 | 94:6 |
11 4 | DABCO | MeCN | 2 | 62 | 10 | 71:29 |
12 4 | DABCO | Et2O | 2 | 47 | 48 | 74:26 |
13 4 | DABCO | CH2Cl2 | 2 | 57 | 9 | 84:16 |
14 4 | DABCO | MeOH | 2 | 0 | 55 | – |
Entry | Catalyst | Solvent | Time (h) | Yield (%) 2 | dr 3 | %ee 4 (Major/Minor) | |
---|---|---|---|---|---|---|---|
2a | 3a | ||||||
1 | C1 | toluene | 31 | 25 | 50 | 73:27 | 0/0 |
2 | C2 | toluene | 10 | 99 | 0 | 92:8 | –41/–28 |
3 | C3 | toluene | 7 | 91 | 6 | 93:7 | –33/–22 |
4 | C4 | toluene | 9 | 89 | 0 | 94:6 | 50/33 |
5 | C5 | toluene | 3 | 80 | 10 | 94:6 | 44/31 |
6 | C6 | toluene | 5 | 88 | 3 | 90:10 | –45/–63 |
7 | C7 | toluene | 33 | 40 | 53 | 74:26 | –2/0 |
8 | C8 | toluene | 1 | 83 | 10 | 92:8 | 5/44 |
9 | C9 | toluene | 0.5 | 96 | 4 | 94:6 | 33/58 |
10 | C4 | THF | 4 | 99 | 0 | 93:7 | 57/35 |
11 | C4 | CH2Cl2 | 7 | 89 | 8 | 92:8 | 65/32 |
12 | C4 | MeCN | 10 | 98 | 0 | 92:8 | 73/42 |
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Kawanishi, R.; Hattori, S.; Iwasa, S.; Shibatomi, K. Amine-Catalyzed Decarboxylative Aldol Reaction of β-Ketocarboxylic Acids with Trifluoropyruvates. Molecules 2019, 24, 2773. https://doi.org/10.3390/molecules24152773
Kawanishi R, Hattori S, Iwasa S, Shibatomi K. Amine-Catalyzed Decarboxylative Aldol Reaction of β-Ketocarboxylic Acids with Trifluoropyruvates. Molecules. 2019; 24(15):2773. https://doi.org/10.3390/molecules24152773
Chicago/Turabian StyleKawanishi, Ryouta, Shinya Hattori, Seiji Iwasa, and Kazutaka Shibatomi. 2019. "Amine-Catalyzed Decarboxylative Aldol Reaction of β-Ketocarboxylic Acids with Trifluoropyruvates" Molecules 24, no. 15: 2773. https://doi.org/10.3390/molecules24152773