title: Selecting the Most Appropriate NMR Experiment to Access Weak and/or Very Long-Range Heteronuclear Correlations.
abstract: Heteronuclear long-range NMR experiments are well established as essential NMR techniques for the structure elucidation of unknown natural products and small molecules. It is generally accepted that the absence of a given (n)JXH correlation in an HMBC or HSQMBC spectrum would automatically place the proton at least four bonds away from the carbon in question. This assumption can, however, be misleading in the case of a mismatch between the actual coupling constant and the delay used to optimize the experiment, which can lead to structural misassignments. Another scenario arises when an investigator, for whatever reason, needs to have access to very long-range correlations to confirm or refute a structure. In such cases, a conventional HMBC experiment will most likely fail to provide the requisite correlation, regardless of the delay optimization. Two recent methods for visualizing extremely weak or very long-range connectivities are the LR-HSQMBC and the HSQMBC-TOCSY experiments. Although they are intended to provide similar structural information, they utilize different transfer mechanisms, which differentiates the experiments, making each better suited for specific classes of compounds. In this report we have sought to examine the considerations implicit in choosing the best experiment to access weak or very long-range correlations for different types of molecules.
authors.affiliation: NMR Structure Elucidation, Process & Analytical Chemistry, Merck & Co. Inc. , 126 E. Lincoln Avenue, Rahway, New Jersey 07065, United States.
authors.forename: Josep
authors.initials: J
authors.lastname: Saurí
authors.affiliation: NMR Structure Elucidation, Process & Analytical Chemistry, Merck & Co. Inc. , 126 E. Lincoln Avenue, Rahway, New Jersey 07065, United States.
authors.forename: Yizhou
authors.initials: Y
authors.lastname: Liu
authors.affiliation: Servei de Ressonància Magnètica Nuclear, Universitat Autònoma de Barcelona , E-08193 Bellaterra, Barcelona, Catalonia, Spain.
authors.forename: Teodor
authors.initials: T
authors.lastname: Parella
authors.affiliation: NMR Structure Elucidation, Process & Analytical Chemistry, Merck & Co. Inc. , 126 E. Lincoln Avenue, Rahway, New Jersey 07065, United States.
authors.forename: R Thomas
authors.initials: RT
authors.lastname: Williamson
authors.affiliation: NMR Structure Elucidation, Process & Analytical Chemistry, Merck & Co. Inc. , 126 E. Lincoln Avenue, Rahway, New Jersey 07065, United States.
authors.forename: Gary E
authors.initials: GE
authors.lastname: Martin
mesh_terms: D001688:Biological Products / Q000737:chemistry*; D015394:Molecular Structure; D019906:Nuclear Magnetic Resonance, Biomolecular / Q000379:methods*
chemical_list: D001688:Biological Products