Regioselective and Stereodivergent Synthesis of Enantiomerically Pure Vic-Diamines from Chiral β-Amino Alcohols with 2-Pyridyl and 6-(2,2′-Bipyridyl) Moieties †
Abstract
:1. Introduction
2. Results and Discussion
2.1. Attempted Direct Substitution of the Hydroxyl Group by the External Nucleophile
2.2. Synthesis of Aziridines
2.3. Aziridine Structural Investigation by NMR
2.4. Synthesis of Diamines
2.4.1. Synthesis of Diamines by Ring Opening of Aziridines with Hydrazoic Acid
2.4.2. Synthesis of Diamines by Nucleophilic Substitution of Sulfamidates
2.4.3. Reduction of Azido Amines to Vic-Diamines
3. Materials and Methods
3.1. General
3.2. General Procedure for the Synthesis of Aziridines
3.3. General Procedure for the Synthesis of Cyclic Sulfamidates
3.4. Synthesis of Azides
3.5. General Procedure for the Synthesis of Diamines
4. Conclusions
Supplementary Materials
Author Contributions
Funding
Acknowledgments
Conflicts of Interest
References
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Sample Availability: Samples of the compounds 20–24 are available from the authors. |
Configuration of Amino Alcohol | R1 | R2 | R3 | Configuration of Products | Yield a (%) |
---|---|---|---|---|---|
(1R,1′S)-1 | Ph | H | Ph | (2S,1′S)-8 | 76 |
(1S,1′S)-1 | Ph | H | Ph | (2R,1′S)-8 | 72 |
(1S,1′S)-2 | Py | H | Ph | (2R,1′S)-9 | 45, 82 b |
(1S,2S,1′S)-5 | Py | Ph | Ph | (2R,3S,1′S)-10 | 33, 74 b |
(1R,2R,1′S)-5 | Py | Ph | Ph | (2S,3R,1′S)-10 | 33, 76 b |
(1R,2R,1′R)-6 | Py | Ph | cyclohexyl | (2S,3R,1′R)-11 | 45 |
(1S,2S,1′S)-7 | Bpy | Ph | Ph | (2R,3S,1′S)-12 | 65 |
(1R,2R,1′S)-7 | Bpy | Ph | Ph | (2S,3R,1′S)-12 | 70 |
Signal | DFT δ, ppm | Experiment δ, ppm | ||
---|---|---|---|---|
(1SN)-10 | (1RN)-10 | Major | Minor | |
H-2 | 3.16 | 3.74 | 3.27 | 3.52 |
H-3 | 4.20 | 3.49 | 3.97 | 3.49 |
1-CH | 4.75 | 3.10 | 3.91 | 3.12 |
CH3 | 1.59 | 1.46 | 1.50 | 1.44 |
Configuration of Aziridines | R1 | R2 | Configuration of Azides | Yield of Azides (%) |
---|---|---|---|---|
(2S,1′S)-8 | H | Ph | (1R,1′S)-3 | 97 |
(2R,1′S)-8 | H | Ph | (1S,1′S)-3 | 90 |
(1R,1′S)-9 | H | Py | (2S,1′S)-4 | 93 a |
(2R,3S,1′S)-10 | Ph | Py | (1R,2R,1′S)-13 | 95 |
(2S,3R,1′S)-12 | Ph | Bpy | (1S,2S,1′S)-14 | 94 |
Configuration of Azides | R1 | R2 | Configuration of Diamines | Yield of Diamines (%) |
---|---|---|---|---|
(1R,1′S)-3 | Ph | H | (1R,1′S)-20 | 74 |
(1S,1′S)-4 | Py | H | (1S,1′S)-21 | 75 |
(1R,2R,1′S)-13 | Ph | Py | (1R,2R,1′S)-22 | 60 |
(1S,2S,1′S)-14 | Ph | Bpy | (1S,2S,1′S)-23 | 50 |
(1R,2S,1′S)-19 | Py | Ph | (1R,2S,1′S)-24 | 70 |
(1S,2R,1′S)-19 | Py | Ph | (1S,2R,1′S)-24 | 73 |
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Wosińska-Hrydczuk, M.; Boratyński, P.J.; Skarżewski, J. Regioselective and Stereodivergent Synthesis of Enantiomerically Pure Vic-Diamines from Chiral β-Amino Alcohols with 2-Pyridyl and 6-(2,2′-Bipyridyl) Moieties. Molecules 2020, 25, 727. https://doi.org/10.3390/molecules25030727
Wosińska-Hrydczuk M, Boratyński PJ, Skarżewski J. Regioselective and Stereodivergent Synthesis of Enantiomerically Pure Vic-Diamines from Chiral β-Amino Alcohols with 2-Pyridyl and 6-(2,2′-Bipyridyl) Moieties. Molecules. 2020; 25(3):727. https://doi.org/10.3390/molecules25030727
Chicago/Turabian StyleWosińska-Hrydczuk, Marzena, Przemysław J. Boratyński, and Jacek Skarżewski. 2020. "Regioselective and Stereodivergent Synthesis of Enantiomerically Pure Vic-Diamines from Chiral β-Amino Alcohols with 2-Pyridyl and 6-(2,2′-Bipyridyl) Moieties" Molecules 25, no. 3: 727. https://doi.org/10.3390/molecules25030727