Application of INADEQUATE NMR techniques for directly tracing out the carbon skeleton of a natural product

0543110 - ÚEB 2022 RIV GB eng J - Článek v odborném periodiku
Ismail, F. M.D. - Nahar, Lutfun - Sarker, S. D.
Application of INADEQUATE NMR techniques for directly tracing out the carbon skeleton of a natural product.
Phytochemical Analysis. Roč. 32, č. 1 (2021), s. 7-23. ISSN 0958-0344. E-ISSN 1099-1565
Institucionální podpora: RVO:61389030
Klíčová slova: 13 13 C– C connectivity * 1 J coupling CC * 2d nmr * case/panacea * cryoprobe * inadequate * natural product * structure elucidation
Obor OECD: Technologies involving identifying the functioning of DNA, proteins and enzymes and how they influence the onset of disease and maintenance of well-being (gene-based diagnostics and therapeutic interventions (pharmacogenomics, gene-based therapeutics)
Impakt faktor: 3.024, rok: 2021
Způsob publikování: Open access
http://doi.org/10.1002/pca.2976

Introduction: Nuclear magnetic resonance (NMR) measurement of J coupling by two-dimensional (2D) INADEQUATE (incredible natural abundance double quantum transfer experiment), which is a special case of double-quantum (DQ) spectroscopy that offers unambiguous determination of C– C spin–spin connectivities through the DQ transitions of the spin system, is especially suited to solving structures rich in quaternary carbons and poor in hydrogen content (Crews rule). Objective: To review published literature on the application of NMR methods to determine structure in the liquid-state, which specifically considers the interaction of a pair of carbon-13 ( C) nuclei adjacent to one another, to allow direct tracing out of contiguous carbon connectivity using 2D INADEQUATE. Methodology: A comprehensive literature search was implemented with various databases: Web of Knowledge, PubMed and SciFinder, and other relevant published materials including published monographs. The keywords used, in various combinations, with INADEQUATE being present in all combinations, in the search were 2D NMR, J coupling, natural product, structure elucidation, C– C connectivity, cryoprobe and CASE (computer-assisted structure elucidation)/PANACEA (protons and nitrogen and carbon et alia). Results: The 2D INADEQUATE continues to solve “intractable” problems in natural product chemistry, and using milligram quantities with cryoprobe techniques combined with CASE/PANACEA experiments can increase machine time efficiency. The C– C-based structural elucidation by dissolution single-scan dynamic nuclear polarisation NMR can overcome disadvantages of C insensitivity at natural abundance. Selected examples have demonstrated the trajectory of INADEQUATE spectroscopy from structural determination to clarification of metabolomics analysis and use of DFT (density functional theory) and coupling constants to clarify the connectivity, hybridisation and stereochemistry within natural products. Conclusions: Somewhat neglected over the years because of perceived lack of sensitivity, the 2D INADEQUATE NMR technique has re-emerged as a useful tool for solving natural products structures, which are rich in quaternary carbons and poor in hydrogen content.
Trvalý link: http://hdl.handle.net/11104/0320399