Stereochemistry of complex natural compounds by vibrational optical activity: acetogenins

• Grant number: 16/23794-0
• Support Opportunities: Scholarships in Brazil - Post-Doctoral
• Start date: April 01, 2017
• End date: May 06, 2018
• Field of knowledge: Physical Sciences and Mathematics - Chemistry - Organic Chemistry
• Agreement: Coordination of Improvement of Higher Education Personnel (CAPES)
• Principal Investigator: Quezia Bezerra Cass
• Grantee: Fernando Martins dos Santos Junior
• Host Institution: Centro de Ciências Exatas e de Tecnologia (CCET). Universidade Federal de São Carlos (UFSCAR). São Carlos , SP, Brazil
• Associated research grant: 13/01710-1 - Enzyme ligand: new models of screening, AP.TEM

Abstract

Determining the absolute configuration of chiral molecules is one of the mostchallenging tasks in natural product chemistry due to the structural complexity of secondarymetabolites containing multiple chiral centers. Among the techniques available to assess theirstereochemical properties, chiroptical spectroscopy, which arises from differential interactionof chiral molecules with circularly polarized radiation, is a powerful alternative. OpticalRotation, Optical Rotatory Dispersion, and Electronic Circular Dichroism are chiropticalmethods applied in the UV-visible spectral region. Vibrational Circular Dichroism and RamanOptical activity, on the other hand, are applied in the infrared region and are commonly referredto as Vibrational Optical Activity (VOA). In this project, we focus on the use of VOAtechniques to determine the relative (RC) and absolute (AC) configurations of severalacetogenins isolated from Annona mucosa (Annonaceae). These secondary metabolites presenta broad spectrum of biological activities, including potent pesticide activity, making thempromising candidates as natural insecticides against agricultural plagues in Brazil. However, itis extremely important to determine the exact spatial arrangement of their atoms. Moststereochemical data found in the literature for acetogenins are incomplete, and based primarilyon empirical 1H e 13C NMR analysis. Therefore, this project aims, through the combination oftheoretical and experimental spectroscopic data, to establish definitely the AC of acetogeninsdirectly in solution. The spectral signatures to be identified in this project will be useful in futurestudies of other molecules from the same class. (AU)

Scientific publications

(7)

(References retrieved automatically from Web of Science and SciELO through information on FAPESP grants and their corresponding numbers as mentioned in the publications by the authors)

DE AMORIM, MARCELO R.; HILARIO, FELIPE; DOS SANTOS JUNIOR, FERNANDO M.; BATISTA JUNIOR, JOAOM.; BAUAB, TAIS M.; ARAUJO, ANGELA R.; CARLOS, IRACILDA Z.; VILEGAS, WAGNER; DOS SANTOS, LOURDES C.. New Benzaldehyde and Benzopyran Compounds from the Endophytic Fungus Paraphaeosphaeria sp. F03 and Their Antimicrobial and Cytotoxic Activities {*}. Planta Medica, v. 85, n. 11/12, p. 957-964, AUG 2019. (14/25222-9, 16/23794-0, 15/04899-3, 15/11058-5)

CCANA-CCAPATINTA, GARI V.; SAMPAIO, BRUNO L.; DOS SANTOS, JR., FERNANDO M.; BATISTA, JR., JOAO M.; DA COSTA, FERNANDO B.. Absolute configuration assignment of caffeic acid ester derivatives from Tithonia diversifolia by vibrational circular dichroism: the pitfalls of deuteration. TETRAHEDRON-ASYMMETRY, v. 28, n. 12, p. 1823-1828, DEC 15 2017. (15/07089-2, 11/13361-6, 14/26866-7, 14/25222-9, 14/16850-6, 16/23794-0)

CANZI, EDIONE F.; DOS SANTOS, JR., FERNANDO M.; MENEGHETTI, EMANUELLE K.; SALES MAIA, BEATRIZ HELENA L. N.; BATISTA, JR., JOAO M.. Absolute configuration of a rare dibenzoylmethane derivative from Dahlstedtia glaziovii (Fabaceae). Tetrahedron Letters, v. 59, n. 2, p. 135-137, JAN 10 2018. (16/23794-0, 14/25222-9, 15/07089-2)

DE AMORIM, MARCELO R.; HILARIO, FELIPE; DOS SANTOS JUNIOR, FERNANDO M.; BATISTA JUNIOR, JOAOM.; BAUAB, TAIS M.; ARAUJO, ANGELA R.; CARLOS, IRACILDA Z.; VILEGAS, WAGNER; DOS SANTOS, LOURDES C.. New Benzaldehyde and Benzopyran Compounds from the Endophytic Fungus Paraphaeosphaeria sp. F03 and Their Antimicrobial and Cytotoxic Activities *. Planta Medica, v. 85, n. 11/12, p. 8-pg., 2019-08-01. (15/11058-5, 14/25222-9, 16/23794-0, 15/04899-3)

GIMENES, LEILA; BATISTA JUNIOR, JOAO MARCOS; DOS SANTOS JUNIOR, FERNANDO MARTINS; SOUZA, MATHEUS DA SILVA; LUNA-DULCEY, LIANY; ELLENA, JAVIER ESTEVES; COMINETTI, MARCIA REGINA; DAS GRACAS FERNANDES DA SILVA, MARIA FATIMA; VIEIRA, PAULO CEZAR; FERNANDES, JOAO BATISTA; et al. Picraviane A and B: Nortriterpenes with limonoid-like skeletons containing a heptanolide E-ring system from Picramnia glazioviana. Phytochemistry, v. 163, p. 38-45, JUL 2019. (13/20458-1, 15/07089-2, 16/18024-1, 14/25222-9, 12/25299-6, 16/23794-0)

BATISTA, ANDREA N. L.; DOS SANTOS, JR., FERNANDO M.; BATISTA, JR., JOAO M.; CASS, QUEZIA B.. Enantiomeric Mixtures in Natural Product Chemistry: Separation and Absolute Configuration Assignment. Molecules, v. 23, n. 2, FEB 2018. (13/01710-1, 16/23794-0, 14/25222-9, 15/07089-2)

DOS SANTOS, JR., FERNANDO M.; BICALHO, KEYLLA U.; CALISTO, ITALO H.; SCATENA, GABRIEL S.; FERNANDES, JOAO B.; CASS, QUEZIA B.; BATISTA, JR., JOAO M.. Scope of the 2(5H)-furanone helicity rule: a combined ECD, VCD, and DFT investigation. ORGANIC & BIOMOLECULAR CHEMISTRY, v. 16, n. 24, p. 4509-4516, JUN 28 2018. (15/07089-2, 13/01710-1, 14/25222-9, 10/18832-4, 12/25299-6, 16/23794-0)