Connecting Discrete Stereoclusters by Using DFT and NMR Spectroscopy: The Case of Nivariol

Cen-Pacheco, Francisco; Rodrı́guez, Jaime; Norte, Manuel; Fernández, José J.; Daranas, Antonio Hernández

doi:10.1002/chem.201204272

Cited by 40 publications

(26 citation statements)

References 41 publications

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“…Uemura et al [24] published the structure after crystallization in methanol and the atomic coordinates were downloaded from the Cambridge Crystallographic Data Centre [25] under the accession number CCDC 691258.…”

Section: Resultsmentioning

confidence: 99%

Stereochemistry of Complex Marine Natural Products by Quantum Mechanical Calculations of NMR Chemical Shifts: Solvent and Conformational Effects on Okadaic Acid

Domínguez¹,

Crespín

Santiago-Benítez³

et al. 2014

Marine Drugs

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Marine organisms are an increasingly important source of novel metabolites, some of which have already inspired or become new drugs. In addition, many of these molecules show a high degree of novelty from a structural and/or pharmacological point of view. Structure determination is generally achieved by the use of a variety of spectroscopic methods, among which NMR (nuclear magnetic resonance) plays a major role and determination of the stereochemical relationships within every new molecule is generally the most challenging part in structural determination. In this communication, we have chosen okadaic acid as a model compound to perform a computational chemistry study to predict 1H and 13C NMR chemical shifts. The effect of two different solvents and conformation on the ability of DFT (density functional theory) calculations to predict the correct stereoisomer has been studied.

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Section: Resultsmentioning

confidence: 99%

Stereochemistry of Complex Marine Natural Products by Quantum Mechanical Calculations of NMR Chemical Shifts: Solvent and Conformational Effects on Okadaic Acid

Domínguez¹,

Crespín

Santiago-Benítez³

et al. 2014

Marine Drugs

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“…Regarding the stereoclusters problem, perhaps one of the most significant examples was presented in 2011 by Daranas and co‐workers in the isolation and assignment of nivariol, a new oxasqualenoid from a Macaronesian endemic species of Laurencia viridis . This interesting compound presents two well‐separated stereoclusters (C1–C15 and C18–C24) and within the former, three aditional stereoclusters: C3–C6, C7–C10, and C11–C14, Figure .…”

Section: Dp4mentioning

confidence: 99%

Computational Chemistry to the Rescue: Modern Toolboxes for the Assignment of Complex Molecules by GIAO NMR Calculations

Grimblat

Sarotti

2016

Chemistry A European J

187

147

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The calculations of NMR properties of molecules using quantum chemical methods have deeply impacted several branches of organic chemistry. They are particularly important in structural or stereochemical assignments of organic compounds, with implications in total synthesis, stereoselective reactions, and natural products chemistry. In studying the evolution of the strategies developed to support (or reject) a structural proposal, it becomes clear that the most effective and accurate ones involve sophisticated procedures to correlate experimental and computational data. Owing to their relatively high mathematical complexity, such calculations (CP3, DP4, ANN-PRA) are often carried out using additional computational resources provided by the authors (such as applets or Excel files). This Minireview will cover the state-of-the-art of these toolboxes in the assignment of organic molecules, including mathematical definitions, updates, and discussion of relevant examples.

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“…The challenging relative configurations of the five-membered rings of compounds 1 – 5 were established by our simple and effective J -based methodology [7]. In addition, a detailed study of NMR chemical shifts by DFT calculation analysis was also undertaken with the aim of connecting remote chiralities within these tetrahydrofuranyl-acetogenins [15]. …”

Section: Introductionmentioning

confidence: 99%

Stereochemical Determination of Five-Membered Cyclic Ether Acetogenins Using a Spin-Spin Coupling Constant Approach and DFT Calculations

et al. 2014

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Five-membered rings are of particular interest, due to their presence in some of the most common molecules in chemistry and biology. Despite their apparent simplicity, the structural resolution of these rings is complex, due to their inherent conformational flexibility. Here, we describe an application of a recently reported simple and efficient NMR protocol based on the measurement of spin-spin coupling constants to achieve the challenging relative configurations of five new halogenated C15 tetrahydrofuranyl-acetogenins, marilzafurollenes A–D (1–4) and 12-acetoxy-marilzafurenyne (5), isolated from the red alga, Laurencia marilzae. Although DFT chemical shift calculations were used to connect remote stereocenters, the NMR-based approach seems advantageous over computational techniques in this context, as the presence of halogens may interfere with reliable calculations.

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Connecting Discrete Stereoclusters by Using DFT and NMR Spectroscopy: The Case of Nivariol

Cited by 40 publications

References 41 publications

Stereochemistry of Complex Marine Natural Products by Quantum Mechanical Calculations of NMR Chemical Shifts: Solvent and Conformational Effects on Okadaic Acid

Stereochemistry of Complex Marine Natural Products by Quantum Mechanical Calculations of NMR Chemical Shifts: Solvent and Conformational Effects on Okadaic Acid

Computational Chemistry to the Rescue: Modern Toolboxes for the Assignment of Complex Molecules by GIAO NMR Calculations

Stereochemical Determination of Five-Membered Cyclic Ether Acetogenins Using a Spin-Spin Coupling Constant Approach and DFT Calculations

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