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Open AccessArticle

In Silico Modeling of Spirolides and Gymnodimines: Determination of S Configuration at Butenolide Ring Carbon C-4

1
Department of Ecological Chemistry, Alfred Wegener Institute, Helmholtz Centre for Polar and Marine Research, Am Handelshafen 12, 27570 Bremerhaven, Germany
2
Faculty of Biology and Chemistry, University of Bremen, Leobener Straße 6, 28359 Bremen, Germany
*
Author to whom correspondence should be addressed.
Toxins 2020, 12(11), 685; https://doi.org/10.3390/toxins12110685
Received: 1 October 2020 / Revised: 27 October 2020 / Accepted: 28 October 2020 / Published: 29 October 2020
(This article belongs to the Special Issue Isolation and Characterization of Marine Toxins)
Only few naturally occurring cyclic imines have been fully structurally elucidated or synthesized to date. The configuration at the C-4 carbon plays a pivotal role in the neurotoxicity of many of these metabolites, for example, gymnodomines (GYMs) and spirolides (SPXs). However, the stereochemistry at this position is not accessible by nuclear Overhauser effect—nuclear magnetic resonance spectroscopy (NOE-NMR) due to unconstrained rotation of the single carbon bond between C-4 and C-5. Consequently, the relative configuration of GYMs and SPXs at C-4 and its role in protein binding remains elusive. Here, we determined the stereochemical configuration at carbon C-4 in the butenolide ring of spirolide- and gymnodimine-phycotoxins by comparison of measured 13C NMR shifts with values obtained in silico using force field, semiempirical and density functional theory methods. This comparison demonstrated that modeled data support S configuration at C-4 for all studied SPXs and GYMs, suggesting a biosynthetically conserved relative configuration at carbon C-4 among these toxins. View Full-Text
Keywords: gymnodimines; spirolides; marine biotoxins; stereochemistry; shielding tensors; simulated NMR gymnodimines; spirolides; marine biotoxins; stereochemistry; shielding tensors; simulated NMR
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MDPI and ACS Style

Zurhelle, C.; Harder, T.; Tillmann, U.; Tebben, J. In Silico Modeling of Spirolides and Gymnodimines: Determination of S Configuration at Butenolide Ring Carbon C-4. Toxins 2020, 12, 685.

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