Strategies for absolute configuration assignments of organic molecules aided by first-principles computations
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The absolute configuration assignments of organic molecules by the comparison of experiment with computed chiroptical response are a useful tool in chemistry. However, such assignments are challenging to perform if the molecule has optical rotation less than 100 deg cm 2 /dmol. Two strategies to improve the reliability of such assignments are explored. The pH dependence of the optical rotation and circular dichroism of α–chiral carboxylic acids, the Clough–Lutz–Jirgenson effect , is analyzed at a molecular level. Second, chiroptical ‘sector maps’ are computed for oxirane and enone chromophores, including illustrative examples for their interpretation.