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Emergence of single-molecular chirality from achiral reactants.

Steendam RR, Verkade JM, van Benthem TJ, Meekes H, van Enckevort WJ, Raap J, Rutjes FP, Vlieg E - Nat Commun (2014)

Bottom Line: The synthesis of enantiopure molecules from achiral precursors without the need for pre-existing chirality is a major challenge associated with the origin of life.We here show that an enantiopure product can be obtained from achiral starting materials in a single organic reaction.An essential characteristic of this reaction is that the chiral product precipitates from the solution, introducing a crystal-solution interface which functions as an asymmetric autocatalytic system that provides sufficient chiral amplification to reach an enantiopure end state.

View Article: PubMed Central - PubMed

Affiliation: Institute for Molecules and Materials, Radboud University Nijmegen, Heyendaalseweg 135, 6525 AJ Nijmegen, The Netherlands.

ABSTRACT
The synthesis of enantiopure molecules from achiral precursors without the need for pre-existing chirality is a major challenge associated with the origin of life. We here show that an enantiopure product can be obtained from achiral starting materials in a single organic reaction. An essential characteristic of this reaction is that the chiral product precipitates from the solution, introducing a crystal-solution interface which functions as an asymmetric autocatalytic system that provides sufficient chiral amplification to reach an enantiopure end state. This approach not only provides more insight into the origin of life but also offers a pathway to acquire enantiopure compounds for industrial applications.

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The aza-Michael reaction at a high concentration (0.5 M) in the presence of an achiral catalyst (DBU).(a) Evolution of the reaction in time. The lines are a guide to the eye. (b) Schematic representation of the mechanism behind the reaction.
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f3: The aza-Michael reaction at a high concentration (0.5 M) in the presence of an achiral catalyst (DBU).(a) Evolution of the reaction in time. The lines are a guide to the eye. (b) Schematic representation of the mechanism behind the reaction.

Mentions: To overcome the lack of chiral amplification in solution, crystal–solution interactions were utilized leading to a much stronger chiral amplification. Conducting the reaction at higher concentrations causes precipitation of the product during the reaction. This creates a crystal–solution interface that completely transforms the initial achiral reactants into an enantiopure solid end state. The course of this reaction at higher concentration is shown in Fig. 3a, while the mechanism behind the reaction is indicated in Fig. 3b.


Emergence of single-molecular chirality from achiral reactants.

Steendam RR, Verkade JM, van Benthem TJ, Meekes H, van Enckevort WJ, Raap J, Rutjes FP, Vlieg E - Nat Commun (2014)

The aza-Michael reaction at a high concentration (0.5 M) in the presence of an achiral catalyst (DBU).(a) Evolution of the reaction in time. The lines are a guide to the eye. (b) Schematic representation of the mechanism behind the reaction.
© Copyright Policy - open-access
Related In: Results  -  Collection

License
Show All Figures
getmorefigures.php?uid=PMC4263183&req=5

f3: The aza-Michael reaction at a high concentration (0.5 M) in the presence of an achiral catalyst (DBU).(a) Evolution of the reaction in time. The lines are a guide to the eye. (b) Schematic representation of the mechanism behind the reaction.
Mentions: To overcome the lack of chiral amplification in solution, crystal–solution interactions were utilized leading to a much stronger chiral amplification. Conducting the reaction at higher concentrations causes precipitation of the product during the reaction. This creates a crystal–solution interface that completely transforms the initial achiral reactants into an enantiopure solid end state. The course of this reaction at higher concentration is shown in Fig. 3a, while the mechanism behind the reaction is indicated in Fig. 3b.

Bottom Line: The synthesis of enantiopure molecules from achiral precursors without the need for pre-existing chirality is a major challenge associated with the origin of life.We here show that an enantiopure product can be obtained from achiral starting materials in a single organic reaction.An essential characteristic of this reaction is that the chiral product precipitates from the solution, introducing a crystal-solution interface which functions as an asymmetric autocatalytic system that provides sufficient chiral amplification to reach an enantiopure end state.

View Article: PubMed Central - PubMed

Affiliation: Institute for Molecules and Materials, Radboud University Nijmegen, Heyendaalseweg 135, 6525 AJ Nijmegen, The Netherlands.

ABSTRACT
The synthesis of enantiopure molecules from achiral precursors without the need for pre-existing chirality is a major challenge associated with the origin of life. We here show that an enantiopure product can be obtained from achiral starting materials in a single organic reaction. An essential characteristic of this reaction is that the chiral product precipitates from the solution, introducing a crystal-solution interface which functions as an asymmetric autocatalytic system that provides sufficient chiral amplification to reach an enantiopure end state. This approach not only provides more insight into the origin of life but also offers a pathway to acquire enantiopure compounds for industrial applications.

Show MeSH