Computer-Assisted 3D Structure Elucidation of Natural Products using Residual Dipolar Couplings.

An enhanced computer-assisted procedure for the determination of the relative configuration of natural products, which starts from the molecular formula and uses a combination of conventional 1D and 2D NMR spectra, and residual dipolar couplings (RDCs), is reported. Having already the data acquired (1D/2D NMR and RDCs), the procedure begins with the determination of the molecular constitution using standard computer-assisted structure elucidation (CASE) and is followed by fully automated determination of relative configuration through RDC analysis. In the case of moderately flexible molecules the simplest data-explaining conformational model is selected by the use of the Akaike information criterion.

Self-Sensitized Photooxygenation of 2H-Pyrans: Characterization of Unexpected Products Assisted by Computed Structural Elucidation and Residual Dipolar Couplings.

The UVA (350 nm) irradiation of an α-pyran in the presence of oxygen led to the unexpected formation of a tetraoxygenated compound whose structure could not be unambiguously determined on the basis of conventional (1)H-(13)C correlated experiments. 1,1-ADEQUATE (adequate double quantum transfer experiment) and 1,n-ADEQUATE combined with computer-assisted structure elucidation software led to two structural possibilities involving the formation of either an epoxide or an oxetane. Residual dipolar couplings allowed not only the identification of the compound as a spiroepoxide but also the determination of its relative configuration.

Disodium cromoglycate: exploiting its properties as a NMR weak-aligning medium for small organic molecules.

Chromonic phases are a family of lyotropic liquid crystals (LC) formed by ionic aromatic mesogens such as disodium cromoglycate (cromolyn), sunset yellow and others. It is well known that chromonic phases are oriented in the presence of external magnetic fields, leading to the observation of anisotropic NMR observables such as quadrupolar splittings or residual dipolar couplings. Despite the fact that the cromolyn nematic LC phase (N) presents important advantages like great homogeneity, small line broadening, and easy sample preparation, it has been scarcely used as a water-compatible NMR orienting medium, in part due to a too strong induced degree of alignment on the guest molecules.

New strategy for RDC-assisted diastereotopic proton assignment using a combination of J-scaled BIRD HSQC and J-scaled BIRD HMQC/HSQC.

A new strategy to assign diastereotopic protons was developed on the basis of residual dipolar couplings (RDCs) collected in compressed poly(methyl methacrylate) (PMMA) gels. A combination of 2D J-scaled BIRD HSQC and J-scaled BIRD HMQC/HSQC NMR experiments was used to collect the RDC data. In the proposed strategy, the first experiment is used to measure (1)D(CH) for methine groups, the sum of (1)D(CHa) + (1)D(CHb) for methylene groups and the average (1)D(CH3) value for methyl groups.