A New Metric for Evaluating DFT Calculated Proton and Carbon Chemical Shifts of Natural Products and Organic Compounds

The calculation of DFT (density functional theory) chemical shifts have become an important technique for the verification of a proposed structure. An easily calculated metric developed for proton and carbon chemical shifts of natural products and organic compounds, the calculated chemical shift index (CCSI), has been developed, which uses the deviation of each pair of calculated and experimental chemical shifts. The mean absolute deviation (MAD), which is commonly used as the goodness of fit metric for DFT calculated chemical shifts, can conceal large deviations in the calculated data. A classification strategy is also proposed for the CCSI to highlight when further assessment of the NMR data is required.     

A minimalist NMR approach for the structural revision of mucoxin

In an attempt to revise the structural assignment of mucoxin, and faced with 64 diastereomeric possibilities, we resorted to the synthesis of truncated structures that contained the core stereochemical sites. Twelve stereochemical analogues were synthesized, their (1)H and (13)C NMR spectra were analyzed and four recurring stereochemical trends were distilled from the data. Applying the observed trends to the diastereomeric population pared the possible choices for the correct structure of mucoxin from 64 to 4. Synthesis of these analogues led to the identification of the correct structure of mucoxin.     

Chemical and Toxicological Investigations of a Previously Unknown Poisonous European Mushroom Tricholoma terreum

The established tradition of consuming and marketing wild mushrooms has focused attention on mycotoxicity, which has become a global issue. In the present study, we describe the toxins found in a previously unknown poisonous European mushroom Tricholoma terreum. Fifteen new triterpenoids terreolides A–F ( 1 – 6 ) and saponaceolides H–P ( 8 – 16 ) were isolated from the fruiting bodies of the toxic mushroom T. terreum. Terreolides A–C ( 1 – 3 ) possessed a unique 5/6/7 trioxaspiroketal system, whereas terreolides D–F ( 4 – 6 ) possessed an unprecedented carbon skeleton. Two abundant compounds in the mushroom, saponaceolide B ( 7 ) and saponaceolide M ( 13 ), displayed acute toxicity, with LD₅₀ values of 88.3 and 63.7 mg kg^?1 when administered orally in mice. Both compounds were found to increase serum creatine kinase levels in mice, indicating that T. terreum may be the cause of mushroom poisoning ultimately leading to rhabdomyolysis.     

Determination of the Absolute Configuration of Super‐Carbon‐Chain Compounds by a Combined Chemical,Spectroscopic, and Computational Approach: Gibbosols A and B

Marine dinoflagellates produce remarkable organic molecules, particularly those with polyoxygenated long‐carbon‐chain backbones, namely super‐carbon‐chain compounds (SCCCs), characterized by the presence of numerous stereogenic carbon centers on acyclic polyol carbon chains. Even today, it is a challenge to determine the absolute configurations of these compounds. In this work, the planar structures and absolute configurations of two highly flexible SCCCs, featuring either a C₆₉‐ or C₇₁‐linear carbon backbone, gibbosols A and B, respectively, each containing thirty‐seven stereogenic carbon centers, were unambiguously established by a combined chemical, spectroscopic, and computational approach. The discovery of gibbosols A and B with two hydrophilic acyclic polyol chains represents an unprecedented class of SCCCs. A reasonable convergent strategy for the biosynthesis of these SCCCs was proposed.     

Toward the complete prediction of the 1H and 13C NMR spectra of complex organic molecules by DFT methods: application to natural substances

The NMR parameters (1H and 13C chemical shifts and coupling constants) for a series of naturally occurring molecules have been calculated mostly with DFT methods, and their spectra compared with available experimental ones. The comparison includes strychnine as a test case, as well as some examples of recently isolated natural products (corianlactone, daphnipaxinin, boletunone B) featuring unusual and/or crowded structures and, in the case of boletunone B, being the subject of a recent revision. Whenever experimental spectra were obtained in polar solvents, the calculation of NMR parameters was also carried out with the Integral Equation-Formalism Polarizable Continuum Model (IEF-PCM) continuum method. The computed results generally show a good agreement with experiment, as judged not only by statistical parameters but also by visual comparison of line spectra. The origin of the remaining discrepancies is attributed to the incomplete modeling of conformational and specific solvent effects.     

Structure and Biosynthetic Assembly of Gulmirecins,Macrolide Antibiotics from the Predatory Bacterium Pyxidicoccus fallax

The gulmirecins constitute a new class of glycosylated macrolides that were isolated from the predatory bacterium Pyxidicoccus fallax HKI 727. Their structures were solved by a combination of NMR spectroscopic experiments and chemical derivatization. Analysis of the annotated gulmirecin gene cluster complemented the configurational assignment and provided insights into the stereochemical course of the biosynthetic assembly. The gulmirecins exhibit strong activity against staphylococci, including methicillin‐resistant Staphylococcus aureus, but no cytotoxic effects on human cells.     

Suffrutines A and B: A Pair of Z/E Isomeric Indolizidine Alkaloids from the Roots of Flueggea suffruticosa

Suffrutines A ( 1 ) and B ( 2 ), a pair of novel photochemical Z/E isomeric indolizidine alkaloids, with a unique and highly conjugated C₂₀ skeleton, were isolated from the roots of Flueggea suffruticosa. The structures were elucidated by extensive analysis of NMR spectra and single‐crystal X‐ray diffraction. The light‐induced isomerization and hypothetical biogenetic pathway to 1 and 2 , as well as their activity for regulating the morphology of Neuro‐2a cells are also discussed.     

Structure characterization and possible biogenesis of three new families of nortriterpenoids: schisanartane, schiartane, and 18-norschiartane

Four new, highly oxygenated nortriterpenoids with unique schisanartane skeletons, micrandilactones D-G (1-4), have been isolated from the leaves and stems of Schisandra micrantha, and their structures have been elucidated on the basis of extensive spectral studies. The postulated biogenetic sequences of sixteen highly oxygenated nortriterpenoids and bisnortriterpenoids with new skeletons from three Schisandra species are discussed and have been compared from a chemotaxonomic standpoint.     

Strength by Joining Methods: Combining Synthesis with NMR,IR, and Vibrational Circular Dichroism Spectroscopy for the Determination of the Relative Configuration in Hemicalide

The relative configuration of a key subunit of hemicalide, a recently isolated, highly bioactive marine natural product having potent antiproliferative activity against a panel of human cancer cell lines, was assigned by combining stereocontrolled synthesis of model substrates with NMR, IR, and vibrational circular dichroism (VCD) spectroscopy. The assignment of the absolute configuration of asymmetric carbon center C42 in two structurally complex epimeric substructures containing six stereocenters by VCD analysis illustrates the power and reliability of combining methods.