PubMed · 7985473
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J Cohen. Gametes micromanipulation.. https://pubmed.ncbi.nlm.nih.gov/7985473/
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[structure--see text] Calyculins A and B differ only by the (E)- vs (Z)-configuration at C(2). Yet, they show a large difference in optical rotations. We demonstrate a new strategy that provides a physical analysis of this long-range chiro-optical effect by Boltzmann-averaged atomic contribution mapping. The polarizability characteristics of the CN substituent rather than the perturbation of the stereogenic centers or the introduction of asymmetry into the polyene chain give rise to the remarkable difference in rotation angles.
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[reaction: see text] We present two new diffusion-edited NMR experiments, improved DECODES and HETDECODES, that sort the constituents in a mixture by their individual diffusion coefficients. These experiments should allow the partial NMR spectral assignment and cursory structure elucidation of compounds in a complex mixture as an aid in the dereplication of known or nuisance compounds.