Structure-Reactivity Correlations for Solid-State Enantioselective Photochemical Reactions Established Directly from Powder X-ray Diffraction

摘要

Among the wide-ranging areas of interest in organic solid-state photochemistry the drive to achieve asymmetric synthesis has led,inter alia,to the development of the chiral ionic auxiliary approach for generating chiral products from achiral reactant molecules in crystalline solids.However,in many cases of interest,the reactant material does not form single crystals of appropriate size and quality to allow structural properties to be established using single-crystal X-ray diffraction techniques,thus limiting the opportunity to establish structure-reactivity correlations in such cases.In this paper,we demonstrate the successful application of modern powder X-ray diffraction techniques,using the direct space strategy for structure solution,to establish structure-reactivity correlations for enantioselective reactions carried out within a series of photoreactive crystalline materials,focusing in particular on rationalization of the enantiomeric excesses (ee) observed in these reactions.