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Probing long-range anisotropic interactions – A general and sign-sensitive strategy to measure 1H-1H residual dipolar couplings as a key advance for organic structure determination

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posted on 2020-01-17, 15:26 authored by Davy SinnaeveDavy Sinnaeve, Julian Ilgen, Maria Enrica Di Pietro, Johann J. Primozic, Volker Schmidts, Christina M. Thiele, Burkhard Luy

Raw Bruker NMR data associated with the publication in Angewandte Chemie International Edition, 2020, DOI: 10.1002/anie.201915278

Residual dipolar couplings (RDCs) are amongst the most powerful NMR parameters for organic structure elucidation. In order to maximize their effectiveness in increasingly complex cases such as flexible compounds, a maximum of RDCs between nuclei sampling a large distribution of orientations is needed, including sign information. For this, the easily accessible one-bond 1H-13C RDCs alone often fall short. Long-range 1H-1H RDCs are both abundant and typically sample highly complementary orientations, but accessing them in a sign-sensitive way has been severely obstructed due to the overflow of 1H-1H couplings. Here, we present a generally applicable strategy that allows the measurement of a large number of 1H-1H RDCs, including the sign, that is based on a combination of the PSYCHEDELIC method and a new selective constant-time beta-COSY experiment. The potential of 1H-1H RDCs to better determine molecular alignment and to discriminate between enantiomers and diastereomers is demonstrated.