Isotopically Directed Symmetry Breaking and Enantioenrichment in Attrition-Enhanced Deracemization

The evolution of homochirality via attrition-enhanced deracemization (AED) of enantiomorphic solids is carried out using molecules that differ only in the isotopic composition of a phenyl group positioned remote from the chiral center. Enantioenrichment consistently favors the enantiomorph containin...

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Bibliographic Details
Published in:Journal of the American Chemical Society 2020-02, Vol.142 (8), p.3873-3879
Main Authors: Murray, James I, Sanders, Jacob N, Richardson, Paul F, Houk, K. N, Blackmond, Donna G
Format: Article
Language:English
Subjects:
Isotopes - chemistry
Molecular Structure
Solubility
Stereoisomerism
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Summary:The evolution of homochirality via attrition-enhanced deracemization (AED) of enantiomorphic solids is carried out using molecules that differ only in the isotopic composition of a phenyl group positioned remote from the chiral center. Enantioenrichment consistently favors the enantiomorph containing a deuterated phenyl group over the protio or 13C version, and the protio version is consistently favored over the 13C version. While these isotopic compounds exhibit identical crystal structures and solubilities, the trend in deracemization correlates with melting points. Understanding the origin of this isotope bias provides fundamental clues about overcoming stochastic behavior to direct the stereochemical outcome in attrition-enhanced deracemization processes. The energy required for breaking symmetry with chiral bias is compared for this near-equilibrium AED process and the far-from-equilibrium Soai autocatalytic reaction. Implications for the origin of biological homochirality are discussed.
ISSN:0002-7863
1520-5126
DOI:10.1021/jacs.9b11422