Chiral β-Amino Alcohols as Ligands for the Ruthenium-Catalyzed Asymmetric Transfer Hydrogenation of N-Phosphinyl Ketimines
Abstract
:1. Introduction
2. Experimental Section
2.1. General
2.2. Procedure for the Preparation of N-Phosphinylimines 1
2.3. Procedure for the Asymmetric Transfer Hydrogenation of Imines 1
3. Results and Discussion
Entry | Ru-dimer (mol%) | L1(mol%) | Base | T (°C) | t (h) | Product 2a | ||
---|---|---|---|---|---|---|---|---|
Base | mol% | Yield b (%) | ee c (%) | |||||
1 | 5 | 20 | KOH | 50 | 25 | 5 | 56 | 66 |
2 | 5 | 10 | KOH | 50 | 25 | 3 | 76 | 72 |
3 | 5 | 5 | KOH | 50 | 25 | 6 | 55 | 64 |
4 | 5 | 10 | KOH | 75 | 25 | 3 | 84 | 66 |
5 | 5 | 10 | KOH | 25 | 25 | 6 | 78 | 66 |
6 | 5 | 10 | LiOH | 50 | 25 | 5 | 63 | 70 |
7 | 5 | 10 | NaOH | 50 | 25 | 3 | 55 | 68 |
8 | 3 | 6 | KOH | 30 | 25 | 18 | 53 | 74 |
9 | 5 | 10 | KOH | 50 | 50 | 2 | 74 | 60 |
10 | 5 | 10 | KOH | 50 | 0 | 29 | 48 | 78 |
11 d | 5 | 10 | KOH | 50 | 0 to 25 | 19 | 70 | 78 |
12 d | 5 | 10 | KOH | 50 | −20 to 25 | 22 | 80 | 80 |
13 d | 5 | 10 | t-BuOK | 50 | −20 to 25 | 20 | 87 | 82 |
14 d | 5 | 10 | t-BuOK | 50 | −40 to 25 | 20 | 85 | 78 |
Entry | Imine | Ligand | t (h) | Product 2 | ||||
---|---|---|---|---|---|---|---|---|
No. | R1 | R2 | No. | Yield b (%) | ee c (%) | |||
1 | 1a | H | Me | L1 | 20 | 2a | 87 | 82 |
2 | 1a | H | Me | L2 | 20 | 2a | 49 | 48 |
3 | 1a | H | Me | L3 | 20 | 2a | 39 | 53 |
4 | 1a | H | Me | L4 | 22 | 2a | — d | — |
5 | 1a | H | Me | L5 | 25 | 2a | — e | — |
6 | 1b | H | Et | L1 | 20 | 2b | 90 | 82 |
7 | 1c | Cl | Me | L1 | 20 | 2c | 85 | 80 |
4. Conclusions
Acknowledgements
References and Notes
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Pablo, Ó.; Guijarro, D.; Yus, M. Chiral β-Amino Alcohols as Ligands for the Ruthenium-Catalyzed Asymmetric Transfer Hydrogenation of N-Phosphinyl Ketimines. Appl. Sci. 2012, 2, 1-12. https://doi.org/10.3390/app2010001
Pablo Ó, Guijarro D, Yus M. Chiral β-Amino Alcohols as Ligands for the Ruthenium-Catalyzed Asymmetric Transfer Hydrogenation of N-Phosphinyl Ketimines. Applied Sciences. 2012; 2(1):1-12. https://doi.org/10.3390/app2010001
Chicago/Turabian StylePablo, Óscar, David Guijarro, and Miguel Yus. 2012. "Chiral β-Amino Alcohols as Ligands for the Ruthenium-Catalyzed Asymmetric Transfer Hydrogenation of N-Phosphinyl Ketimines" Applied Sciences 2, no. 1: 1-12. https://doi.org/10.3390/app2010001