α(δ')-Michael Addition of Alkyl Amines to Dimethyl (E)-hex-2-en-4-ynedioate: Synthesis of α,β-Dehydroamino Acid Derivatives
Abstract
:1. Introduction
2. Results and Discussion
Entry | Amine | Solvent | Reaction conditions | Yields of 4 (%) b | |
---|---|---|---|---|---|
(2E,4E) | (2Z,4E) | ||||
1 | n-Octylamine | THF | rt | 82 | 00 |
2 | n-Octylamine | THF | 60 °C | 81 | 00 |
3 | n-Octylamine | Benzene | rt | 52 | 00 |
4 | n-Octylamine | Toluene | rt | 49 | 00 |
5 | n-Octylamine | DCM | rt | 46 | 00 |
6 | n-Octylamine | MeCN | rt | 65 | 00 |
7 | Piperidine | THF | rt | 64 | 16 |
8 | Piperidine | THF | 60 °C | 54 | 14 |
9 | Piperidine | Benzene | rt | 68 | 11 |
10 | Piperidine | Toluene | rt | 60 (68) | 08 (09) |
11 | Piperidine | DCM | rt | 58 (63) | 12 (13) |
12 | Piperidine | MeCN | rt | 48 (51) | 08 (09) |
Entry | R1 | Product (2E,4E) | Yield (%) b |
---|---|---|---|
1 | n-Hexyl-3a | 67 | |
2 | n-Octyl-3b | 82 | |
3 | n-Decyl-3c | 73 | |
4 | n-Dodecyl-3d | 73 | |
5 c | Benzyl- 3e | 73 (75) c | |
6 | iso-Propyl-3f | 60 (64) | |
7 | tert-Butyl-3g | 25 (58) | |
8 | Allyl- 3h | 68 | |
9 | Ethanol- 3i | 78 (80) |
Entry | R1R2 | Major Product (2E,4E) | Yield (%) b | Minor Product (2Z,4E) | Yield (%) b | Ratio of (2E,4E)/(2Z,4E) |
---|---|---|---|---|---|---|
1 | Diethyl 3j | 53 (58) | 14 (15) | 3.8:1 | ||
2 | Dipropyl 3k | 59 (62) | 16 (17) | 3.7:1 | ||
3 | Pyrrolidine 3l | 56 | 18 | 3.1:1 | ||
4 | Piperidine 3m | 64 | 16 | 4:1 | ||
5 | Morpholine 3n | 58 | 18 | 3.2:1 |
3. Experimental
3.1. General
3.2. General Experimental Procedure for Reactions with Primary Alkyl Amines
3.3. General Experimental Procedure for Reactions with Secondary Alkyl Amines
4. Conclusions
Supplementary Materials
Acknowledgments
References
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Chavan, A.S.; Deng, J.-C.; Chuang, S.-C. α(δ')-Michael Addition of Alkyl Amines to Dimethyl (E)-hex-2-en-4-ynedioate: Synthesis of α,β-Dehydroamino Acid Derivatives. Molecules 2013, 18, 2611-2622. https://doi.org/10.3390/molecules18032611
Chavan AS, Deng J-C, Chuang S-C. α(δ')-Michael Addition of Alkyl Amines to Dimethyl (E)-hex-2-en-4-ynedioate: Synthesis of α,β-Dehydroamino Acid Derivatives. Molecules. 2013; 18(3):2611-2622. https://doi.org/10.3390/molecules18032611
Chicago/Turabian StyleChavan, Arjun S., Jie-Cheng Deng, and Shih-Ching Chuang. 2013. "α(δ')-Michael Addition of Alkyl Amines to Dimethyl (E)-hex-2-en-4-ynedioate: Synthesis of α,β-Dehydroamino Acid Derivatives" Molecules 18, no. 3: 2611-2622. https://doi.org/10.3390/molecules18032611