Structural characterisation of natural products by means of quantum chemical calculations of NMR parameters: new insights

Costa, Fábio Luiz Paranhos; Albuquerque, Ana Carolina Ferreira de; Fiorot, Rodolfo G.; Lião, Luciano M.; Martorano, Lucas H.; Mota, Gunar Vingre da Silva; Valverde, Alessandra L.; Carneiro, José Walkimar de M.; Santos, Fernando Martins dos

doi:10.1039/d1qo00034a

Cited by 55 publications

(53 citation statements)

References 193 publications

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“…Este é um trabalho teórico-experimental, onde a molécula foco do estudo é a savinina, uma lignana do tipo dibenzilbutirolactônica, substâncias que pode ser encontrada em diversos gêneros, um dos quais possui maior ocorrência é o gênero Acanthopanax (Araliaceae) que é tradicionalmente usado como analgésico e estimulante do sistema imunológico, além de exibir um potente atividade inseticida e citotóxica para células HCT116 de carcinoma do cólon humano [26]. Ela foi isolada e aqui apresentamos a sua caracterização experimental e teórica por meio de dados de RMN de 13 C e 1 H e a possível confirmação da estrutura utilizando a ferramenta rede neural (ANN-PRA) [27,28].…”

Section: Introductionunclassified

Uma Investigação Sobre a Ideia De Número

Ribeiro¹,

Silva²,

Bergamaschi³

et al. 2022

Avanços Dos Estudos Científicos Na Área Das Ciências Exatas

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Section: Introductionunclassified

Uma Investigação Sobre a Ideia De Número

Ribeiro¹,

Silva²,

Bergamaschi³

et al. 2022

Avanços Dos Estudos Científicos Na Área Das Ciências Exatas

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“…[ 4,5 ] The computational simulations of 1 H and 13 C NMR chemical shifts and spin–spin coupling constants ( J ) registered a marked increase in precision, accessibility and application, leading to a more precise spectral interpretation. [ 4,5 ] Thus, in addition to aiding the structure elucidation of new natural products, computational methods have been of great utility in helping to uncover and ultimately revise the structure of previously reported compounds, leading to a considerable advance in the field of natural products. [ 4–11 ]…”

Section: Introductionmentioning

confidence: 99%

“…[ 4,5 ] Thus, in addition to aiding the structure elucidation of new natural products, computational methods have been of great utility in helping to uncover and ultimately revise the structure of previously reported compounds, leading to a considerable advance in the field of natural products. [ 4–11 ]…”

Section: Introductionmentioning

confidence: 99%

“…[ 17 ] Considering that the structures of some compounds of the Heliannuol family have been reassigned previously, [ 21 ] the reexamination of the proposed structure of Heliannuol L is of interest. Following our continuous pursuit of the application and development of new tools to the structural elucidation of complex natural products by means of quantum chemical calculations of NMR parameters, [ 5,22–29 ] in this article, we discuss the first analysis of the stereoisomers of Heliannuol L and propose a revision of its relative configuration.…”

Section: Introductionmentioning

confidence: 99%

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Revisiting the structure of Heliannuol L: A computational approach

Martorano

Brito

Albuquerque

et al. 2021

Magnetic Reson in Chemistry

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Recently, structural elucidation of natural products has undergone a revolution. The combined use of different modern spectroscopic methods has allowed obtaining a complete structural assignment of natural products using small amounts of sample. However, despite the extraordinary ongoing advances in spectroscopy, the mischaracterization of natural products has been and remains a recurrent problem, especially when the substance presents several stereogenic centers. The misinterpretation of nuclear magnetic resonance (NMR) data has resulted in frequent reports addressing structural reassignment. In this context, a great effort has been devoted to developing quantum chemical calculations that simulate NMR parameters accurately, allowing to achieve a more precise spectral interpretation. In this work, we employed a protocol for theoretical calculations of 1H NMR chemical shifts and coupling constants using density functional theory (DFT), followed by the application of the DP4+ method to revisit the structure of Heliannuol L, a member of the Heliannuol class, isolated from Helianthus annuus. Our results indicate that the originally proposed structure of Heliannuol L needs a stereochemical reassignment, placing the hydroxyl bonded to C10 in the opposite side of the methyl and hydroxyl groups bonded to C7 and C8, respectively.

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“…The wide variety of pharmacological effects of medicinal plants can be attributed to their specialized metabolites. Originally, most natural products were isolated from terrestrial plants, but nowadays, it is very common to isolate and identify compounds also from (micro)organisms of both terrestrial and marine environments (Colegate and Molyneux 2008;Koskinen 2012;Carroll et al 2020). From the data presented in a recent review, natural product chemistry, associated with synthesis and biology, still offers the best options for finding new agents or active models in drug discovery (Newman and Cragg 2020).…”

Section: Introductionmentioning

confidence: 99%

Vibrational Circular Dichroism for the Assignment of Absolute Configuration of Natural Products in Brazil

Batista

Valverde

Batista

2021

Rev. Bras. Farmacogn.

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The determination of the absolute configuration of chiral bioactive natural products is a crucial step in their structural characterization. Several well-established techniques, such as X-ray crystallography, stereo-controlled organic synthesis, NMR, and chiroptical spectroscopy, are commonly used to this end. However, even today, the configurational analysis of natural products remains a challenge, with a significant number of reassignments being reported every year. Among chiroptical methods, vibrational circular dichroism (VCD) has emerged as an excellent tool for the assignment of the absolute configuration of structurally diverse chiral natural products directly in solution. This review covers the use of VCD spectroscopy to elucidate the absolute stereochemistry of natural products in Brazil over the last 20 years. Although the number of VCD investigations on secondary metabolites has increased, VCD can still be considered under-explored in Brazil. Therefore, herein, we aim to demonstrate the unparalleled stereochemical discriminatory power of VCD to assign both conformation and absolute configuration of natural products in conditions not commonly accessible to other techniques.

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Structural characterisation of natural products by means of quantum chemical calculations of NMR parameters: new insights

Abstract: The calculation of NMR parameters for natural products was pioneered by Bifulco and coworkers in 2002. Since then, modelling 1H and 13C chemical shifts and spin-spin coupling constants for this...

Cited by 55 publications

References 193 publications

Uma Investigação Sobre a Ideia De Número

Uma Investigação Sobre a Ideia De Número

Revisiting the structure of Heliannuol L: A computational approach

Vibrational Circular Dichroism for the Assignment of Absolute Configuration of Natural Products in Brazil

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