deracemization and related processes · 2020. 1. 15. · 2002, 41, 3177. kroutil, w.; faber, k....
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![Page 1: Deracemization and Related Processes · 2020. 1. 15. · 2002, 41, 3177. Kroutil, W.; Faber, K. Tetrahedron: Asymmetry 1998, 9, 2901. Deracemization is inherently endothermic due](https://reader035.vdocuments.net/reader035/viewer/2022070218/61268d845c00f9279f0b9043/html5/thumbnails/1.jpg)
Deracemization and Related Processes
Kevin Wu
13 January 2019
Yu Group
![Page 2: Deracemization and Related Processes · 2020. 1. 15. · 2002, 41, 3177. Kroutil, W.; Faber, K. Tetrahedron: Asymmetry 1998, 9, 2901. Deracemization is inherently endothermic due](https://reader035.vdocuments.net/reader035/viewer/2022070218/61268d845c00f9279f0b9043/html5/thumbnails/2.jpg)
Asymmetric Catalysis – Known Strategies
Noyori, R.; Ohkuma, T. Angew. Chem. Int. Ed. 2001, 40, 40.
Sharpless, K. B.; et al. J. Org. Chem. 1992, 57, 2768.
List, B.; Lerner, R. A; Barbas, C. F. J. Am. Chem. Soc. 2000, 122, 2395.
Selective reaction with a prochiral, planar precursor is a common strategy in asymmetric catalysis:
![Page 3: Deracemization and Related Processes · 2020. 1. 15. · 2002, 41, 3177. Kroutil, W.; Faber, K. Tetrahedron: Asymmetry 1998, 9, 2901. Deracemization is inherently endothermic due](https://reader035.vdocuments.net/reader035/viewer/2022070218/61268d845c00f9279f0b9043/html5/thumbnails/3.jpg)
Asymmetric Catalysis – Known Strategies
Noyori, R.; Ohkuma, T. Angew. Chem. Int. Ed. 2001, 40, 40.
Sharpless, K. B.; et al. J. Org. Chem. 1992, 57, 2768.
List, B.; Lerner, R. A; Barbas, C. F. J. Am. Chem. Soc. 2000, 122, 2395.
Selective reaction with a prochiral, planar precursor is a common strategy in asymmetric catalysis:
![Page 4: Deracemization and Related Processes · 2020. 1. 15. · 2002, 41, 3177. Kroutil, W.; Faber, K. Tetrahedron: Asymmetry 1998, 9, 2901. Deracemization is inherently endothermic due](https://reader035.vdocuments.net/reader035/viewer/2022070218/61268d845c00f9279f0b9043/html5/thumbnails/4.jpg)
Asymmetric Catalysis – Known Strategies
Noyori, R.; Ohkuma, T. Angew. Chem. Int. Ed. 2001, 40, 40.
Sharpless, K. B.; et al. J. Org. Chem. 1992, 57, 2768.
List, B.; Lerner, R. A; Barbas, C. F. J. Am. Chem. Soc. 2000, 122, 2395.
Selective reaction with a prochiral, planar precursor is a common strategy in asymmetric catalysis:
![Page 5: Deracemization and Related Processes · 2020. 1. 15. · 2002, 41, 3177. Kroutil, W.; Faber, K. Tetrahedron: Asymmetry 1998, 9, 2901. Deracemization is inherently endothermic due](https://reader035.vdocuments.net/reader035/viewer/2022070218/61268d845c00f9279f0b9043/html5/thumbnails/5.jpg)
Asymmetric Catalysis – Known Strategies
Noyori, R.; Ohkuma, T. Angew. Chem. Int. Ed. 2001, 40, 40.
Sharpless, K. B.; et al. J. Org. Chem. 1992, 57, 2768.
List, B.; Lerner, R. A; Barbas, C. F. J. Am. Chem. Soc. 2000, 122, 2395.
Selective reaction with a prochiral, planar precursor is a common strategy in asymmetric catalysis:
![Page 6: Deracemization and Related Processes · 2020. 1. 15. · 2002, 41, 3177. Kroutil, W.; Faber, K. Tetrahedron: Asymmetry 1998, 9, 2901. Deracemization is inherently endothermic due](https://reader035.vdocuments.net/reader035/viewer/2022070218/61268d845c00f9279f0b9043/html5/thumbnails/6.jpg)
Asymmetric Catalysis – (Dynamic) Kinetic Resolutions
Keith, J. M.; Larrow, J. F.; Jacobsen, E. N. Adv. Synth. Catal. 2001, 343, 5.
Kinetic resolution and dynamic kinetic resolutions also have been well-established:
![Page 7: Deracemization and Related Processes · 2020. 1. 15. · 2002, 41, 3177. Kroutil, W.; Faber, K. Tetrahedron: Asymmetry 1998, 9, 2901. Deracemization is inherently endothermic due](https://reader035.vdocuments.net/reader035/viewer/2022070218/61268d845c00f9279f0b9043/html5/thumbnails/7.jpg)
Asymmetric Catalysis – (Dynamic) Kinetic Resolutions
Keith, J. M.; Larrow, J. F.; Jacobsen, E. N. Adv. Synth. Catal. 2001, 343, 5.
Kinetic resolution and dynamic kinetic resolutions also have been well-established:
![Page 8: Deracemization and Related Processes · 2020. 1. 15. · 2002, 41, 3177. Kroutil, W.; Faber, K. Tetrahedron: Asymmetry 1998, 9, 2901. Deracemization is inherently endothermic due](https://reader035.vdocuments.net/reader035/viewer/2022070218/61268d845c00f9279f0b9043/html5/thumbnails/8.jpg)
Asymmetric Catalysis – (Dynamic) Kinetic Resolutions
Keith, J. M.; Larrow, J. F.; Jacobsen, E. N. Adv. Synth. Catal. 2001, 343, 5.
Kinetic resolution and dynamic kinetic resolutions also have been well-established:
![Page 9: Deracemization and Related Processes · 2020. 1. 15. · 2002, 41, 3177. Kroutil, W.; Faber, K. Tetrahedron: Asymmetry 1998, 9, 2901. Deracemization is inherently endothermic due](https://reader035.vdocuments.net/reader035/viewer/2022070218/61268d845c00f9279f0b9043/html5/thumbnails/9.jpg)
Asymmetric Catalysis – (Dynamic) Kinetic Resolutions
Keith, J. M.; Larrow, J. F.; Jacobsen, E. N. Adv. Synth. Catal. 2001, 343, 5.
Kinetic resolution and dynamic kinetic resolutions also have been well-established:
In an ideal kinetic resolution (s is high)
50% of (S) will remain at 100% ee
![Page 10: Deracemization and Related Processes · 2020. 1. 15. · 2002, 41, 3177. Kroutil, W.; Faber, K. Tetrahedron: Asymmetry 1998, 9, 2901. Deracemization is inherently endothermic due](https://reader035.vdocuments.net/reader035/viewer/2022070218/61268d845c00f9279f0b9043/html5/thumbnails/10.jpg)
Asymmetric Catalysis – (Dynamic) Kinetic Resolutions
Hayashi, T.; Kumada, M.; et al. J. Am. Chem. Soc. 1982, 104, 180.
Cherney, A. H.; Kadunce, N.T.; Reisman, S. E. Chem. Rev. 2015, 115, 9587.
Bhat, V.; Welin, E. R.; Guo, X.; Stotlz, B. M. Chem. Rev. 2017, 117, 4528.
Kinetic resolution and dynamic kinetic resolutions also have been well-established:
![Page 11: Deracemization and Related Processes · 2020. 1. 15. · 2002, 41, 3177. Kroutil, W.; Faber, K. Tetrahedron: Asymmetry 1998, 9, 2901. Deracemization is inherently endothermic due](https://reader035.vdocuments.net/reader035/viewer/2022070218/61268d845c00f9279f0b9043/html5/thumbnails/11.jpg)
Asymmetric Catalysis – (Dynamic) Kinetic Resolutions
Hayashi, T.; Kumada, M.; et al. J. Am. Chem. Soc. 1982, 104, 180.
Cherney, A. H.; Kadunce, N.T.; Reisman, S. E. Chem. Rev. 2015, 115, 9587.
Bhat, V.; Welin, E. R.; Guo, X.; Stotlz, B. M. Chem. Rev. 2017, 117, 4528.
Kinetic resolution and dynamic kinetic resolutions also have been well-established:
![Page 12: Deracemization and Related Processes · 2020. 1. 15. · 2002, 41, 3177. Kroutil, W.; Faber, K. Tetrahedron: Asymmetry 1998, 9, 2901. Deracemization is inherently endothermic due](https://reader035.vdocuments.net/reader035/viewer/2022070218/61268d845c00f9279f0b9043/html5/thumbnails/12.jpg)
Asymmetric Catalysis – (Dynamic) Kinetic Resolutions
Hayashi, T.; Kumada, M.; et al. J. Am. Chem. Soc. 1982, 104, 180.
Cherney, A. H.; Kadunce, N.T.; Reisman, S. E. Chem. Rev. 2015, 115, 9587.
Bhat, V.; Welin, E. R.; Guo, X.; Stotlz, B. M. Chem. Rev. 2017, 117, 4528.
Kinetic resolution and dynamic kinetic resolutions also have been well-established:
![Page 13: Deracemization and Related Processes · 2020. 1. 15. · 2002, 41, 3177. Kroutil, W.; Faber, K. Tetrahedron: Asymmetry 1998, 9, 2901. Deracemization is inherently endothermic due](https://reader035.vdocuments.net/reader035/viewer/2022070218/61268d845c00f9279f0b9043/html5/thumbnails/13.jpg)
Asymmetric Catalysis – Enantioconvergent Reactions
Fu, G. C. ACS Cent. Sci. 2017, 3, 692.
Enantioconvergent reactions are distinct from DKR because they proceed through a prochiral or
configurationally unstable intermediate during catalysis, as opposed to prior racemization
![Page 14: Deracemization and Related Processes · 2020. 1. 15. · 2002, 41, 3177. Kroutil, W.; Faber, K. Tetrahedron: Asymmetry 1998, 9, 2901. Deracemization is inherently endothermic due](https://reader035.vdocuments.net/reader035/viewer/2022070218/61268d845c00f9279f0b9043/html5/thumbnails/14.jpg)
Asymmetric Catalysis – Enantioconvergent Reactions
Fu, G. C. ACS Cent. Sci. 2017, 3, 692.
Enantioconvergent reactions are distinct from DKR because they proceed through a prochiral or
configurationally unstable intermediate during catalysis, as opposed to prior racemization
![Page 15: Deracemization and Related Processes · 2020. 1. 15. · 2002, 41, 3177. Kroutil, W.; Faber, K. Tetrahedron: Asymmetry 1998, 9, 2901. Deracemization is inherently endothermic due](https://reader035.vdocuments.net/reader035/viewer/2022070218/61268d845c00f9279f0b9043/html5/thumbnails/15.jpg)
Asymmetric Catalysis – Enantioconvergent Reactions
Fu, G. C. ACS Cent. Sci. 2017, 3, 692.
Enantioconvergent reactions are distinct from DKR because they proceed through a prochiral or
configurationally unstable intermediate during catalysis, as opposed to prior racemization
![Page 16: Deracemization and Related Processes · 2020. 1. 15. · 2002, 41, 3177. Kroutil, W.; Faber, K. Tetrahedron: Asymmetry 1998, 9, 2901. Deracemization is inherently endothermic due](https://reader035.vdocuments.net/reader035/viewer/2022070218/61268d845c00f9279f0b9043/html5/thumbnails/16.jpg)
Asymmetric Catalysis – Enantioconvergent Reactions
Trost, B. M.; Toste, F. D. J. Am. Chem. Soc. 1999, 121, 3543.
Enantioconvergent reactions are distinct from DKR because they proceed through a prochiral or
configurationally unstable intermediate during catalysis, as opposed to prior racemization
![Page 17: Deracemization and Related Processes · 2020. 1. 15. · 2002, 41, 3177. Kroutil, W.; Faber, K. Tetrahedron: Asymmetry 1998, 9, 2901. Deracemization is inherently endothermic due](https://reader035.vdocuments.net/reader035/viewer/2022070218/61268d845c00f9279f0b9043/html5/thumbnails/17.jpg)
Asymmetric Catalysis – Enantioconvergent Reactions
Trost, B. M.; Toste, F. D. J. Am. Chem. Soc. 1999, 121, 3543.
Enantioconvergent reactions are distinct from DKR because they proceed through a prochiral or
configurationally unstable intermediate during catalysis, as opposed to prior racemization
![Page 18: Deracemization and Related Processes · 2020. 1. 15. · 2002, 41, 3177. Kroutil, W.; Faber, K. Tetrahedron: Asymmetry 1998, 9, 2901. Deracemization is inherently endothermic due](https://reader035.vdocuments.net/reader035/viewer/2022070218/61268d845c00f9279f0b9043/html5/thumbnails/18.jpg)
Deracemization Concepts
Deracemization is inherently endothermic due to the decrease in entropy required:
Kroutil, W.; Faber, K. Tetrahedron: Asymmetry 1998, 9, 2901.
![Page 19: Deracemization and Related Processes · 2020. 1. 15. · 2002, 41, 3177. Kroutil, W.; Faber, K. Tetrahedron: Asymmetry 1998, 9, 2901. Deracemization is inherently endothermic due](https://reader035.vdocuments.net/reader035/viewer/2022070218/61268d845c00f9279f0b9043/html5/thumbnails/19.jpg)
Deracemization Concepts
Deracemization is inherently endothermic due to the decrease in entropy required:
Early strategies used a KR cycling process with an external reagent to drive the cycle:
Kroutil, W.; Faber, K. Tetrahedron: Asymmetry 1998, 9, 2901.
![Page 20: Deracemization and Related Processes · 2020. 1. 15. · 2002, 41, 3177. Kroutil, W.; Faber, K. Tetrahedron: Asymmetry 1998, 9, 2901. Deracemization is inherently endothermic due](https://reader035.vdocuments.net/reader035/viewer/2022070218/61268d845c00f9279f0b9043/html5/thumbnails/20.jpg)
Deracemization Concepts
Deracemization is inherently endothermic due to the decrease in entropy required:
Early strategies used a KR cycling process with an external reagent to drive the cycle:
Kroutil, W.; Faber, K. Tetrahedron: Asymmetry 1998, 9, 2901.
![Page 21: Deracemization and Related Processes · 2020. 1. 15. · 2002, 41, 3177. Kroutil, W.; Faber, K. Tetrahedron: Asymmetry 1998, 9, 2901. Deracemization is inherently endothermic due](https://reader035.vdocuments.net/reader035/viewer/2022070218/61268d845c00f9279f0b9043/html5/thumbnails/21.jpg)
Deracemization Concepts
Deracemization is inherently endothermic due to the decrease in entropy required:
Early strategies used a KR cycling process with an external reagent to drive the cycle:
Repeated cycling leads to the accumulation of (S)
Kroutil, W.; Faber, K. Tetrahedron: Asymmetry 1998, 9, 2901.
![Page 22: Deracemization and Related Processes · 2020. 1. 15. · 2002, 41, 3177. Kroutil, W.; Faber, K. Tetrahedron: Asymmetry 1998, 9, 2901. Deracemization is inherently endothermic due](https://reader035.vdocuments.net/reader035/viewer/2022070218/61268d845c00f9279f0b9043/html5/thumbnails/22.jpg)
Deracemization Concepts
Kroutil, W.; Faber, K. Tetrahedron: Asymmetry 1998, 9, 2901.
Deracemization is inherently endothermic due to the decrease in entropy required:
Early strategies used a KR cycling process with an external reagent to drive the cycle:
![Page 23: Deracemization and Related Processes · 2020. 1. 15. · 2002, 41, 3177. Kroutil, W.; Faber, K. Tetrahedron: Asymmetry 1998, 9, 2901. Deracemization is inherently endothermic due](https://reader035.vdocuments.net/reader035/viewer/2022070218/61268d845c00f9279f0b9043/html5/thumbnails/23.jpg)
Deracemization Concepts: Application of Substrate Cycling
Turner, N. J.; et al. Angew. Chem. Int. Ed. 2002, 41, 3177.
Kroutil, W.; Faber, K. Tetrahedron: Asymmetry 1998, 9, 2901.
Deracemization is inherently endothermic due to the decrease in entropy required:
![Page 24: Deracemization and Related Processes · 2020. 1. 15. · 2002, 41, 3177. Kroutil, W.; Faber, K. Tetrahedron: Asymmetry 1998, 9, 2901. Deracemization is inherently endothermic due](https://reader035.vdocuments.net/reader035/viewer/2022070218/61268d845c00f9279f0b9043/html5/thumbnails/24.jpg)
Deracemization Concepts: Application of Substrate Cycling
Turner, N. J.; et al. Angew. Chem. Int. Ed. 2002, 41, 3177.
Kroutil, W.; Faber, K. Tetrahedron: Asymmetry 1998, 9, 2901.
Deracemization is inherently endothermic due to the decrease in entropy required:
Early examples typically used the oxidation/reduction cycling of alcohols or amines:
![Page 25: Deracemization and Related Processes · 2020. 1. 15. · 2002, 41, 3177. Kroutil, W.; Faber, K. Tetrahedron: Asymmetry 1998, 9, 2901. Deracemization is inherently endothermic due](https://reader035.vdocuments.net/reader035/viewer/2022070218/61268d845c00f9279f0b9043/html5/thumbnails/25.jpg)
Deracemization Concepts: Application of Substrate Cycling
Turner, N. J.; et al. Angew. Chem. Int. Ed. 2002, 41, 3177.
Kroutil, W.; Faber, K. Tetrahedron: Asymmetry 1998, 9, 2901.
Deracemization is inherently endothermic due to the decrease in entropy required:
Early examples typically used the oxidation/reduction cycling of alcohols or amines:
![Page 26: Deracemization and Related Processes · 2020. 1. 15. · 2002, 41, 3177. Kroutil, W.; Faber, K. Tetrahedron: Asymmetry 1998, 9, 2901. Deracemization is inherently endothermic due](https://reader035.vdocuments.net/reader035/viewer/2022070218/61268d845c00f9279f0b9043/html5/thumbnails/26.jpg)
Deracemization: A Common Pitfall
Deracemization is inherently endothermic due to the decrease in entropy required:
Blackmond, D. G. Angew. Chem. Int. Ed. 2009, 48, 2648.
Kroutil, W.; Faber, K. Tetrahedron: Asymmetry 1998, 9, 2901.
![Page 27: Deracemization and Related Processes · 2020. 1. 15. · 2002, 41, 3177. Kroutil, W.; Faber, K. Tetrahedron: Asymmetry 1998, 9, 2901. Deracemization is inherently endothermic due](https://reader035.vdocuments.net/reader035/viewer/2022070218/61268d845c00f9279f0b9043/html5/thumbnails/27.jpg)
Deracemization: A Common Pitfall
Deracemization is inherently endothermic due to the decrease in entropy required:
The concept of substrate cycling has prompted numerous proposals using closed systems:
Blackmond, D. G. Angew. Chem. Int. Ed. 2009, 48, 2648.
Kroutil, W.; Faber, K. Tetrahedron: Asymmetry 1998, 9, 2901.
![Page 28: Deracemization and Related Processes · 2020. 1. 15. · 2002, 41, 3177. Kroutil, W.; Faber, K. Tetrahedron: Asymmetry 1998, 9, 2901. Deracemization is inherently endothermic due](https://reader035.vdocuments.net/reader035/viewer/2022070218/61268d845c00f9279f0b9043/html5/thumbnails/28.jpg)
Deracemization: A Common Pitfall
Deracemization is inherently endothermic due to the decrease in entropy required:
The concept of substrate cycling has prompted numerous proposals using closed systems:
Blackmond, D. G. Angew. Chem. Int. Ed. 2009, 48, 2648.
Kroutil, W.; Faber, K. Tetrahedron: Asymmetry 1998, 9, 2901.
![Page 29: Deracemization and Related Processes · 2020. 1. 15. · 2002, 41, 3177. Kroutil, W.; Faber, K. Tetrahedron: Asymmetry 1998, 9, 2901. Deracemization is inherently endothermic due](https://reader035.vdocuments.net/reader035/viewer/2022070218/61268d845c00f9279f0b9043/html5/thumbnails/29.jpg)
Deracemization: A Common Pitfall
Deracemization is inherently endothermic due to the decrease in entropy required:
The concept of substrate cycling has prompted numerous proposals using closed systems:
Experimental tests inevitably result in racemic mixtures
Blackmond, D. G. Angew. Chem. Int. Ed. 2009, 48, 2648.
Kroutil, W.; Faber, K. Tetrahedron: Asymmetry 1998, 9, 2901.
![Page 30: Deracemization and Related Processes · 2020. 1. 15. · 2002, 41, 3177. Kroutil, W.; Faber, K. Tetrahedron: Asymmetry 1998, 9, 2901. Deracemization is inherently endothermic due](https://reader035.vdocuments.net/reader035/viewer/2022070218/61268d845c00f9279f0b9043/html5/thumbnails/30.jpg)
Deracemization: A Common Pitfall
Deracemization is inherently endothermic due to the decrease in entropy required:
The concept of substrate cycling has prompted numerous proposals using closed systems:
Experimental tests inevitably result in racemic mixtures
The positive ΔG of deracemization immediately shows these
ideas are impossible
Yet these proposals remained common
Blackmond, D. G. Angew. Chem. Int. Ed. 2009, 48, 2648.
Kroutil, W.; Faber, K. Tetrahedron: Asymmetry 1998, 9, 2901.
![Page 31: Deracemization and Related Processes · 2020. 1. 15. · 2002, 41, 3177. Kroutil, W.; Faber, K. Tetrahedron: Asymmetry 1998, 9, 2901. Deracemization is inherently endothermic due](https://reader035.vdocuments.net/reader035/viewer/2022070218/61268d845c00f9279f0b9043/html5/thumbnails/31.jpg)
Deracemization: A Common Pitfall
Deracemization is inherently endothermic due to the decrease in entropy required:
The concept of substrate cycling has prompted numerous proposals using closed systems:
Experimental tests inevitably result in racemic mixtures
The positive ΔG of deracemization immediately shows these
ideas are impossible
Yet these proposals remained common
To understand why such proposals are infeasible, the
principle of microscopic reversibility must be considered
Blackmond, D. G. Angew. Chem. Int. Ed. 2009, 48, 2648.
Kroutil, W.; Faber, K. Tetrahedron: Asymmetry 1998, 9, 2901.
![Page 32: Deracemization and Related Processes · 2020. 1. 15. · 2002, 41, 3177. Kroutil, W.; Faber, K. Tetrahedron: Asymmetry 1998, 9, 2901. Deracemization is inherently endothermic due](https://reader035.vdocuments.net/reader035/viewer/2022070218/61268d845c00f9279f0b9043/html5/thumbnails/32.jpg)
Deracemization: The Principle of Microscopic Reversibility
Blackmond, D. G. Angew. Chem. Int. Ed. 2009, 48, 2648.
The principle of microscopic reversibility states:
![Page 33: Deracemization and Related Processes · 2020. 1. 15. · 2002, 41, 3177. Kroutil, W.; Faber, K. Tetrahedron: Asymmetry 1998, 9, 2901. Deracemization is inherently endothermic due](https://reader035.vdocuments.net/reader035/viewer/2022070218/61268d845c00f9279f0b9043/html5/thumbnails/33.jpg)
Deracemization: The Principle of Microscopic Reversibility
Blackmond, D. G. Angew. Chem. Int. Ed. 2009, 48, 2648.
The principle of microscopic reversibility states:
At equilibrium, any molecular process and the reverse of that process occur at the same rate
![Page 34: Deracemization and Related Processes · 2020. 1. 15. · 2002, 41, 3177. Kroutil, W.; Faber, K. Tetrahedron: Asymmetry 1998, 9, 2901. Deracemization is inherently endothermic due](https://reader035.vdocuments.net/reader035/viewer/2022070218/61268d845c00f9279f0b9043/html5/thumbnails/34.jpg)
Deracemization: The Principle of Microscopic Reversibility
Blackmond, D. G. Angew. Chem. Int. Ed. 2009, 48, 2648.
The principle of microscopic reversibility states:
At equilibrium, any molecular process and the reverse of that process occur at the same rate
Accordingly, the reaction path in the reverse must be the reverse of the forward reaction
![Page 35: Deracemization and Related Processes · 2020. 1. 15. · 2002, 41, 3177. Kroutil, W.; Faber, K. Tetrahedron: Asymmetry 1998, 9, 2901. Deracemization is inherently endothermic due](https://reader035.vdocuments.net/reader035/viewer/2022070218/61268d845c00f9279f0b9043/html5/thumbnails/35.jpg)
Deracemization: The Principle of Microscopic Reversibility
Blackmond, D. G. Angew. Chem. Int. Ed. 2009, 48, 2648.
The principle of microscopic reversibility states:
At equilibrium, any molecular process and the reverse of that process occur at the same rate
Accordingly, the reaction path in the reverse must be the reverse of the forward reaction
Thus the reverse reaction of a catalytic step must proceed via the catalytic path:
![Page 36: Deracemization and Related Processes · 2020. 1. 15. · 2002, 41, 3177. Kroutil, W.; Faber, K. Tetrahedron: Asymmetry 1998, 9, 2901. Deracemization is inherently endothermic due](https://reader035.vdocuments.net/reader035/viewer/2022070218/61268d845c00f9279f0b9043/html5/thumbnails/36.jpg)
Deracemization: The Principle of Microscopic Reversibility
Blackmond, D. G. Angew. Chem. Int. Ed. 2009, 48, 2648.
The principle of microscopic reversibility states:
At equilibrium, any molecular process and the reverse of that process occur at the same rate
Accordingly, the reaction path in the reverse must be the reverse of the forward reaction
Thus the reverse reaction of a catalytic step must proceed via the catalytic path:
The lowest path backward must always
be identical to the lowest path forward
![Page 37: Deracemization and Related Processes · 2020. 1. 15. · 2002, 41, 3177. Kroutil, W.; Faber, K. Tetrahedron: Asymmetry 1998, 9, 2901. Deracemization is inherently endothermic due](https://reader035.vdocuments.net/reader035/viewer/2022070218/61268d845c00f9279f0b9043/html5/thumbnails/37.jpg)
Deracemization: Applying the Principle of Microscopic Reversibility
When considered from this perspective, the issue with closed system recycling is clear:
Blackmond, D. G. Angew. Chem. Int. Ed. 2009, 48, 2648.
![Page 38: Deracemization and Related Processes · 2020. 1. 15. · 2002, 41, 3177. Kroutil, W.; Faber, K. Tetrahedron: Asymmetry 1998, 9, 2901. Deracemization is inherently endothermic due](https://reader035.vdocuments.net/reader035/viewer/2022070218/61268d845c00f9279f0b9043/html5/thumbnails/38.jpg)
Deracemization: Applying the Principle of Microscopic Reversibility
When considered from this perspective, the issue with closed system recycling is clear:
Blackmond, D. G. Angew. Chem. Int. Ed. 2009, 48, 2648.
![Page 39: Deracemization and Related Processes · 2020. 1. 15. · 2002, 41, 3177. Kroutil, W.; Faber, K. Tetrahedron: Asymmetry 1998, 9, 2901. Deracemization is inherently endothermic due](https://reader035.vdocuments.net/reader035/viewer/2022070218/61268d845c00f9279f0b9043/html5/thumbnails/39.jpg)
Deracemization: Applying the Principle of Microscopic Reversibility
When considered from this perspective, the issue with closed system recycling is clear:
Blackmond, D. G. Angew. Chem. Int. Ed. 2009, 48, 2648.
![Page 40: Deracemization and Related Processes · 2020. 1. 15. · 2002, 41, 3177. Kroutil, W.; Faber, K. Tetrahedron: Asymmetry 1998, 9, 2901. Deracemization is inherently endothermic due](https://reader035.vdocuments.net/reader035/viewer/2022070218/61268d845c00f9279f0b9043/html5/thumbnails/40.jpg)
Deracemization: Applying the Principle of Microscopic Reversibility
When considered from this perspective, the issue with closed system recycling is clear:
“Attempts to recycle a catalytic reaction back by its uncatalyzed route clearly breaks the rules”
Blackmond, D. G. Angew. Chem. Int. Ed. 2009, 48, 2648.
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Deracemization: Applying the Principle of Microscopic Reversibility
When considered from this perspective, the issue with closed system recycling is clear:
Blackmond, D. G. Angew. Chem. Int. Ed. 2009, 48, 2648.
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Deracemization: Applying the Principle of Microscopic Reversibility
When considered from this perspective, the issue with closed system recycling is clear:
Blackmond, D. G. Angew. Chem. Int. Ed. 2009, 48, 2648.
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Deracemization: Applying the Principle of Microscopic Reversibility
When considered from this perspective, the issue with closed system recycling is clear:
The energetics that favor the catalytic conversion of the undesired (R)-enantiomer also will favor its
re-formation from the intermediate (if kR is large, then kRb must also be)
The closed system will inexorably proceed towards equilibrium (racemization)
Blackmond, D. G. Angew. Chem. Int. Ed. 2009, 48, 2648.
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Deracemization: Overcoming the Limitations of Closed Systems
To overcome the limitation of a closed systems, a source of chemical or light energy is needed
Knowles, R. R.; et al. Science 2019, 366, 364.
Blackmond, D. G. Angew. Chem. Int. Ed. 2009, 48, 2648.
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Deracemization: Overcoming the Limitations of Closed Systems
To overcome the limitation of a closed systems, a source of chemical or light energy is needed
The principle of microscopic reversibility prohibits a single catalytic step from deracemizing a
reaction
Two or more steps proceeding through distinct mechanisms are necessary
Knowles, R. R.; et al. Science 2019, 366, 364.
Blackmond, D. G. Angew. Chem. Int. Ed. 2009, 48, 2648.
![Page 46: Deracemization and Related Processes · 2020. 1. 15. · 2002, 41, 3177. Kroutil, W.; Faber, K. Tetrahedron: Asymmetry 1998, 9, 2901. Deracemization is inherently endothermic due](https://reader035.vdocuments.net/reader035/viewer/2022070218/61268d845c00f9279f0b9043/html5/thumbnails/46.jpg)
Deracemization: Overcoming the Limitations of Closed Systems
To overcome the limitation of a closed systems, a source of chemical or light energy is needed
The principle of microscopic reversibility prohibits a single catalytic step from deracemizing a
reaction
Two or more steps proceeding through distinct mechanisms are necessary
Chemical compatibility of reagents can be a challenge, especially in redox cycling
Temporal separation is one possible solution (stepwise reactions)
Photochemical methods would be ideal, but few candidate systems exist
Knowles, R. R.; et al. Science 2019, 366, 364.
Blackmond, D. G. Angew. Chem. Int. Ed. 2009, 48, 2648.
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Deracemization: Phase Separation and Chemical Energy
Lackner, A. D.; Samant; A. V.; Toste, F. D. J. Am Chem Soc. 2013, 135, 14090.
Catalytic enantioselective reduction of imines with chiral phosphoric acids is well known:
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Deracemization: Phase Separation and Chemical Energy
Lackner, A. D.; Samant; A. V.; Toste, F. D. J. Am Chem Soc. 2013, 135, 14090.
Catalytic enantioselective reduction of imines with chiral phosphoric acids is well known:
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Deracemization: Phase Separation and Chemical Energy
Lackner, A. D.; Samant; A. V.; Toste, F. D. J. Am Chem Soc. 2013, 135, 14090.
Catalytic enantioselective reduction of imines with chiral phosphoric acids is well known:
The Toste group found CPAs can facilitate phase-transfer oxidation of indolines, with low selectivity
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Deracemization: Phase Separation and Chemical Energy
This phase transfer system appeared suited for a deracemization strategy:
Lackner, A. D.; Samant; A. V.; Toste, F. D. J. Am Chem Soc. 2013, 135, 14090.
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Deracemization: Phase Separation and Chemical Energy
This phase transfer system appeared suited for a deracemization strategy:
Lackner, A. D.; Samant; A. V.; Toste, F. D. J. Am Chem Soc. 2013, 135, 14090.
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Deracemization: Phase Separation and Chemical Energy
This phase transfer system appeared suited for a deracemization strategy:
However, no deuterium erosion (no reaction) was observed when the two cycles were combined:
Lackner, A. D.; Samant; A. V.; Toste, F. D. J. Am Chem Soc. 2013, 135, 14090.
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Deracemization: Phase Separation and Chemical Energy
While the two reagents were insoluble, they were consuming each other in the solid phase:
Lackner, A. D.; Samant; A. V.; Toste, F. D. J. Am Chem Soc. 2013, 135, 14090.
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Deracemization: Phase Separation and Chemical Energy
While the two reagents were insoluble, they were consuming each other in the solid phase:
Therefore, a three-phase strategy (solid, organic, and aqueous) was devised:
Lackner, A. D.; Samant; A. V.; Toste, F. D. J. Am Chem Soc. 2013, 135, 14090.
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Deracemization: Phase Separation and Chemical Energy
Evaluation of several solvent mixtures as well as Hantzsch esters variants showed promise:
Lackner, A. D.; Samant; A. V.; Toste, F. D. J. Am Chem Soc. 2013, 135, 14090.
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Deracemization: Phase Separation and Chemical Energy
Evaluation of several solvent mixtures as well as Hantzsch esters variants showed promise:
Lackner, A. D.; Samant; A. V.; Toste, F. D. J. Am Chem Soc. 2013, 135, 14090.
![Page 57: Deracemization and Related Processes · 2020. 1. 15. · 2002, 41, 3177. Kroutil, W.; Faber, K. Tetrahedron: Asymmetry 1998, 9, 2901. Deracemization is inherently endothermic due](https://reader035.vdocuments.net/reader035/viewer/2022070218/61268d845c00f9279f0b9043/html5/thumbnails/57.jpg)
Deracemization: Phase Separation and Chemical Energy
Evaluation of several solvent mixtures as well as Hantzsch esters variants showed promise:
Lackner, A. D.; Samant; A. V.; Toste, F. D. J. Am Chem Soc. 2013, 135, 14090.
![Page 58: Deracemization and Related Processes · 2020. 1. 15. · 2002, 41, 3177. Kroutil, W.; Faber, K. Tetrahedron: Asymmetry 1998, 9, 2901. Deracemization is inherently endothermic due](https://reader035.vdocuments.net/reader035/viewer/2022070218/61268d845c00f9279f0b9043/html5/thumbnails/58.jpg)
Deracemization: Phase Separation and Chemical Energy
Evaluation of several solvent mixtures as well as Hantzsch esters variants showed promise:
Lackner, A. D.; Samant; A. V.; Toste, F. D. J. Am Chem Soc. 2013, 135, 14090.
![Page 59: Deracemization and Related Processes · 2020. 1. 15. · 2002, 41, 3177. Kroutil, W.; Faber, K. Tetrahedron: Asymmetry 1998, 9, 2901. Deracemization is inherently endothermic due](https://reader035.vdocuments.net/reader035/viewer/2022070218/61268d845c00f9279f0b9043/html5/thumbnails/59.jpg)
Deracemization: Photochemical excitation of axially chiral molecules
Rodriguez, O.; Morrison, H. Chem. Comm. D. 1971, 373, 679.
Bach, T.; et al. Nature 2018, 564, 240.
The racemization of axially chiral allenes via a triplet state is well known:
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Deracemization: Photochemical excitation of axially chiral molecules
Rodriguez, O.; Morrison, H. Chem. Comm. D. 1971, 373, 679.
Bach, T.; et al. Nature 2018, 564, 240.
The racemization of axially chiral allenes via a triplet state is well known:
![Page 61: Deracemization and Related Processes · 2020. 1. 15. · 2002, 41, 3177. Kroutil, W.; Faber, K. Tetrahedron: Asymmetry 1998, 9, 2901. Deracemization is inherently endothermic due](https://reader035.vdocuments.net/reader035/viewer/2022070218/61268d845c00f9279f0b9043/html5/thumbnails/61.jpg)
Deracemization: Photochemical excitation of axially chiral molecules
Rodriguez, O.; Morrison, H. Chem. Comm. D. 1971, 373, 679.
Bach, T.; et al. Nature 2018, 564, 240.
The racemization of axially chiral allenes via a triplet state is well known:
In the presence of a chiral sensitizer, this process could be used to drive deracemization
![Page 62: Deracemization and Related Processes · 2020. 1. 15. · 2002, 41, 3177. Kroutil, W.; Faber, K. Tetrahedron: Asymmetry 1998, 9, 2901. Deracemization is inherently endothermic due](https://reader035.vdocuments.net/reader035/viewer/2022070218/61268d845c00f9279f0b9043/html5/thumbnails/62.jpg)
Deracemization: Photochemical excitation of axially chiral molecules
Rodriguez, O.; Morrison, H. Chem. Comm. D. 1971, 373, 679.
Bach, T.; et al. Nature 2018, 564, 240.
The racemization of axially chiral allenes via a triplet state is well known:
In the presence of a chiral sensitizer, this process could be used to drive deracemization
Continuous cycling of substrate will lead to accumulation of (S)
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Deracemization: Photochemical excitation of axially chiral molecules
Bach, T.; et al. Nature 2018, 564, 240.
This transformation is a variant of the recycling concept, but with the diradical as intermediate:
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Deracemization: Photochemical excitation of axially chiral molecules
Bach, T.; et al. Nature 2018, 564, 240.
This transformation is a variant of the recycling concept, but with the diradical as intermediate:
Light (the source of energy) and a chiral catalyst selectively form a high energy intermediate that
non-selectively recycles to the racemic substrate:
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Allene Deracemization Background: Enantioselective Photosensitization
Bauer, A.; Westkamper, F.; Grimme, S.; Bach, T. Nature 2005, 436, 1139.
Bach, T.; et al. Nature 2018, 564, 240.
Bach had developed an enantioselective H-bonding photosensitizer for single electron transfer:
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Allene Deracemization Background: Enantioselective Photosensitization
Bauer, A.; Westkamper, F.; Grimme, S.; Bach, T. Nature 2005, 436, 1139.
Bach, T.; et al. Nature 2018, 564, 240.
Bach had developed an enantioselective H-bonding photosensitizer for single electron transfer:
![Page 67: Deracemization and Related Processes · 2020. 1. 15. · 2002, 41, 3177. Kroutil, W.; Faber, K. Tetrahedron: Asymmetry 1998, 9, 2901. Deracemization is inherently endothermic due](https://reader035.vdocuments.net/reader035/viewer/2022070218/61268d845c00f9279f0b9043/html5/thumbnails/67.jpg)
Allene Deracemization Background: Enantioselective Photosensitization
Bauer, A.; Westkamper, F.; Grimme, S.; Bach, T. Nature 2005, 436, 1139.
Bach, T.; et al. Nature 2018, 564, 240.
Bach had developed an enantioselective H-bonding photosensitizer for single electron transfer:
![Page 68: Deracemization and Related Processes · 2020. 1. 15. · 2002, 41, 3177. Kroutil, W.; Faber, K. Tetrahedron: Asymmetry 1998, 9, 2901. Deracemization is inherently endothermic due](https://reader035.vdocuments.net/reader035/viewer/2022070218/61268d845c00f9279f0b9043/html5/thumbnails/68.jpg)
Allene Deracemization Background: Enantioselective Photosensitization
Bauer, A.; Westkamper, F.; Grimme, S.; Bach, T. Nature 2005, 436, 1139.
Bach, T.; et al. Nature 2018, 564, 240.
Bach had developed an enantioselective H-bonding photosensitizer for single electron transfer:
H-bonding holds the substrate near the sensitizer, promoting the key SET in a chiral environment
![Page 69: Deracemization and Related Processes · 2020. 1. 15. · 2002, 41, 3177. Kroutil, W.; Faber, K. Tetrahedron: Asymmetry 1998, 9, 2901. Deracemization is inherently endothermic due](https://reader035.vdocuments.net/reader035/viewer/2022070218/61268d845c00f9279f0b9043/html5/thumbnails/69.jpg)
Bach had developed an enantioselective H-bonding photosensitizer for single electron transfer:
H-bonding holds the substrate near the sensitizer, promoting the key SET in a chiral environment
Allene Deracemization Background: Enantioselective Photosensitization
Bauer, A.; Westkamper, F.; Grimme, S.; Bach, T. Nature 2005, 436, 1139.
Bach, T.; et al. Nature 2018, 564, 240.
![Page 70: Deracemization and Related Processes · 2020. 1. 15. · 2002, 41, 3177. Kroutil, W.; Faber, K. Tetrahedron: Asymmetry 1998, 9, 2901. Deracemization is inherently endothermic due](https://reader035.vdocuments.net/reader035/viewer/2022070218/61268d845c00f9279f0b9043/html5/thumbnails/70.jpg)
The concept of hydrogen-bonding chiral recognition could be used to selectively sensitize allenes
Allene Deracemization: Reaction Design
Bach, T.; et al. Nature 2018, 564, 240.
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The concept of hydrogen-bonding chiral recognition could be used to selectively sensitize allenes
Allene Deracemization: Reaction Design
Bach, T.; et al. Nature 2018, 564, 240.
![Page 72: Deracemization and Related Processes · 2020. 1. 15. · 2002, 41, 3177. Kroutil, W.; Faber, K. Tetrahedron: Asymmetry 1998, 9, 2901. Deracemization is inherently endothermic due](https://reader035.vdocuments.net/reader035/viewer/2022070218/61268d845c00f9279f0b9043/html5/thumbnails/72.jpg)
The concept of hydrogen-bonding chiral recognition could be used to selectively sensitize allenes
Allene Deracemization: Reaction Design
Bach, T.; et al. Nature 2018, 564, 240.
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The concept of hydrogen-bonding chiral recognition could be used to selectively sensitize allenes
Allene Deracemization: Reaction Design and Implementation
Bach, T.; et al. Nature 2018, 564, 240.
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The concept of hydrogen-bonding chiral recognition could be used to selectively sensitize allenes
Allene Deracemization: Reaction Design and Implementation
Irradiating either enantiomer with catalyst results in rapid formation of the preferred enantiomer:
Bach, T.; et al. Nature 2018, 564, 240.
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The concept of hydrogen-bonding chiral recognition could be used to selectively sensitize allenes
Allene Deracemization: Substrate Scope
Bach, T.; et al. Nature 2018, 564, 240.
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Knowles observed unexpected product enantioenrichment under PCET hydroamination conditions
Deracemization of Ureas via Excited-State Electron Transfer
Miller, D. C.; Choi, G. J.; Orbe, H. S.; Knowles, R. R. J. Am. Chem. Soc. 2015, 137, 13492.
Knowles, R. R.; et al. Science 2019, 366, 364.
![Page 77: Deracemization and Related Processes · 2020. 1. 15. · 2002, 41, 3177. Kroutil, W.; Faber, K. Tetrahedron: Asymmetry 1998, 9, 2901. Deracemization is inherently endothermic due](https://reader035.vdocuments.net/reader035/viewer/2022070218/61268d845c00f9279f0b9043/html5/thumbnails/77.jpg)
Knowles observed unexpected product enantioenrichment under PCET hydroamination conditions
Deracemization of Ureas via Excited-State Electron Transfer
Miller, D. C.; Choi, G. J.; Orbe, H. S.; Knowles, R. R. J. Am. Chem. Soc. 2015, 137, 13492.
Knowles, R. R.; et al. Science 2019, 366, 364.
![Page 78: Deracemization and Related Processes · 2020. 1. 15. · 2002, 41, 3177. Kroutil, W.; Faber, K. Tetrahedron: Asymmetry 1998, 9, 2901. Deracemization is inherently endothermic due](https://reader035.vdocuments.net/reader035/viewer/2022070218/61268d845c00f9279f0b9043/html5/thumbnails/78.jpg)
The potential for a deracemization approach was then recognized:
Deracemization of Ureas: Design Strategy
Knowles, R. R.; et al. Science 2019, 366, 364.
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The potential for a deracemization approach was then recognized:
Deracemization of Ureas: Design Strategy
Knowles, R. R.; et al. Science 2019, 366, 364.
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The potential for enantioselective HAT to regenerate the substrate was also recognized :
Deracemization of Ureas: Design Strategy
Knowles, R. R.; et al. Science 2019, 366, 364.
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Knowles observed unexpected product enantioenrichment under PCET hydroamination conditions
Deracemization of Ureas: Design Strategy
Knowles, R. R.; et al. Science 2019, 366, 364.
![Page 82: Deracemization and Related Processes · 2020. 1. 15. · 2002, 41, 3177. Kroutil, W.; Faber, K. Tetrahedron: Asymmetry 1998, 9, 2901. Deracemization is inherently endothermic due](https://reader035.vdocuments.net/reader035/viewer/2022070218/61268d845c00f9279f0b9043/html5/thumbnails/82.jpg)
Use of a chiral phosphate and chiral thiol together gave the highest selectivity
Deracemization of Ureas: Catalyst Evaluation
Knowles, R. R.; et al. Science 2019, 366, 364.
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Use of a chiral phosphate and chiral thiol together gave the highest selectivity
Deracemization of Ureas: Catalyst Evaluation
Knowles, R. R.; et al. Science 2019, 366, 364.
![Page 84: Deracemization and Related Processes · 2020. 1. 15. · 2002, 41, 3177. Kroutil, W.; Faber, K. Tetrahedron: Asymmetry 1998, 9, 2901. Deracemization is inherently endothermic due](https://reader035.vdocuments.net/reader035/viewer/2022070218/61268d845c00f9279f0b9043/html5/thumbnails/84.jpg)
Use of a chiral phosphate and chiral thiol together gave the highest selectivity
Deracemization of Ureas: Catalyst Evaluation
Knowles, R. R.; et al. Science 2019, 366, 364.
![Page 85: Deracemization and Related Processes · 2020. 1. 15. · 2002, 41, 3177. Kroutil, W.; Faber, K. Tetrahedron: Asymmetry 1998, 9, 2901. Deracemization is inherently endothermic due](https://reader035.vdocuments.net/reader035/viewer/2022070218/61268d845c00f9279f0b9043/html5/thumbnails/85.jpg)
This system was also capable of performing selective stereoinversion:
Deracemization of Ureas: Stereoinversion
Knowles, R. R.; et al. Science 2019, 366, 364.
![Page 86: Deracemization and Related Processes · 2020. 1. 15. · 2002, 41, 3177. Kroutil, W.; Faber, K. Tetrahedron: Asymmetry 1998, 9, 2901. Deracemization is inherently endothermic due](https://reader035.vdocuments.net/reader035/viewer/2022070218/61268d845c00f9279f0b9043/html5/thumbnails/86.jpg)
This system was also capable of performing selective stereoinversion:
Deracemization of Ureas: Stereoinversion
Knowles, R. R.; et al. Science 2019, 366, 364.
![Page 87: Deracemization and Related Processes · 2020. 1. 15. · 2002, 41, 3177. Kroutil, W.; Faber, K. Tetrahedron: Asymmetry 1998, 9, 2901. Deracemization is inherently endothermic due](https://reader035.vdocuments.net/reader035/viewer/2022070218/61268d845c00f9279f0b9043/html5/thumbnails/87.jpg)
Conclusion
Deracemization has recently seen increased activity as a field of asymmetric catalysis
![Page 88: Deracemization and Related Processes · 2020. 1. 15. · 2002, 41, 3177. Kroutil, W.; Faber, K. Tetrahedron: Asymmetry 1998, 9, 2901. Deracemization is inherently endothermic due](https://reader035.vdocuments.net/reader035/viewer/2022070218/61268d845c00f9279f0b9043/html5/thumbnails/88.jpg)
Conclusion
Deracemization has recently seen increased activity as a field of asymmetric catalysis
Light is a particularly promising energy source to drive selective formation of a single enantiomer
![Page 89: Deracemization and Related Processes · 2020. 1. 15. · 2002, 41, 3177. Kroutil, W.; Faber, K. Tetrahedron: Asymmetry 1998, 9, 2901. Deracemization is inherently endothermic due](https://reader035.vdocuments.net/reader035/viewer/2022070218/61268d845c00f9279f0b9043/html5/thumbnails/89.jpg)
Conclusion
Deracemization has recently seen increased activity as a field of asymmetric catalysis
Light is a particularly promising energy source to drive selective formation of a single enantiomer
![Page 90: Deracemization and Related Processes · 2020. 1. 15. · 2002, 41, 3177. Kroutil, W.; Faber, K. Tetrahedron: Asymmetry 1998, 9, 2901. Deracemization is inherently endothermic due](https://reader035.vdocuments.net/reader035/viewer/2022070218/61268d845c00f9279f0b9043/html5/thumbnails/90.jpg)
Conclusion
Deracemization has recently seen increased activity as a field of asymmetric catalysis
Light is a particularly promising energy source to drive selective formation of a single enantiomer
![Page 91: Deracemization and Related Processes · 2020. 1. 15. · 2002, 41, 3177. Kroutil, W.; Faber, K. Tetrahedron: Asymmetry 1998, 9, 2901. Deracemization is inherently endothermic due](https://reader035.vdocuments.net/reader035/viewer/2022070218/61268d845c00f9279f0b9043/html5/thumbnails/91.jpg)
Conclusion
Deracemization has recently seen increased activity as a field of asymmetric catalysis
Light is a particularly promising energy source to drive selective formation of a single enantiomer
Considerable limitations remain with regards to substrate scope and synthetic utility
![Page 92: Deracemization and Related Processes · 2020. 1. 15. · 2002, 41, 3177. Kroutil, W.; Faber, K. Tetrahedron: Asymmetry 1998, 9, 2901. Deracemization is inherently endothermic due](https://reader035.vdocuments.net/reader035/viewer/2022070218/61268d845c00f9279f0b9043/html5/thumbnails/92.jpg)
Conclusion
Deracemization has recently seen increased activity as a field of asymmetric catalysis
Light is a particularly promising energy source to drive selective formation of a single enantiomer
Considerable limitations remain with regards to substrate scope and synthetic utility
However, further study of system and catalyst design may result in more practical systems: