Reassignments and Corroborations of Oxo‐Bridged Natural Products Directed by OSE and DU8+ NMR Computation

Structural misassignments of natural products are prevalent in the literature. Developing methods and theoretical concepts to assist those undertaking structural elucidation is therefore of paramount importance, such that biologists and synthetic chemists avoid pursuing phantom chemical entities. He...

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Published inAngewandte Chemie International Edition Vol. 58; no. 21; pp. 7107 - 7112
Main Authors Kutateladze, Andrei G., Krenske, Elizabeth H., Williams, Craig M.
Format Journal Article
LanguageEnglish
Published Germany Wiley Subscription Services, Inc 20.05.2019
EditionInternational ed. in English
Subjects
anti-Bredt olefins
Bredt rule
bridgehead double bonds
Chemists
Natural products
NMR
Nuclear magnetic resonance
Organic chemistry
reassignments
anti-Bredt olefins
bridgehead double bonds
natural products
Bredt rule
reassignments
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Summary:Structural misassignments of natural products are prevalent in the literature. Developing methods and theoretical concepts to assist those undertaking structural elucidation is therefore of paramount importance, such that biologists and synthetic chemists avoid pursuing phantom chemical entities. Herein described is a strategy for predicting the isolabilities of oxygen‐substituted bridgehead natural products based on calculations of olefin strain energies, NMR chemical shifts and coupling constants (DU8+). This approach provides corroborating evidence for the structures of certain bridgehead alkene natural products while leading to the reassignment of several other structures. Computationary, my dear Watson! The amalgamation of olefin strain energy (OSE) and DU8+ analysis brings to the fore a powerful combination of in silico methods that can be deployed in concert by those undertaking natural product structure determination.
Bibliography:In memory of Paul von Ragué Schleyer and Julius Bredt
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ISSN:1433-7851
1521-3773
DOI:10.1002/anie.201902777