Systematizing chiroptical properties of lignans: implications for correct absolute configuration assignments

• Grant number: 23/12475-5
• Support Opportunities: Regular Research Grants
• Start date: January 01, 2024
• End date: December 31, 2025
• Field of knowledge: Physical Sciences and Mathematics - Chemistry - Organic Chemistry
• Principal Investigator: João Marcos Batista Junior
• Grantee: João Marcos Batista Junior
• Host Institution: Instituto de Ciência e Tecnologia (ICT). Universidade Federal de São Paulo (UNIFESP). Campus São José dos Campos. São José dos Campos , SP, Brazil
• Associated researchers: Isabele Rodrigues Nascimento
• Associated scholarship(s): 24/17686-7 - Stereochemistry of furofuran lignans from optical rotatory dispersion: interplay between theory and experiment, BP.IC

Abstract

Natural product chemistry deals with organic molecules of high structural and stereochemical complexity of different classes and biosynthetic origins. The main techniques used in structural elucidation/determination, mass spectrometry (MS) and magnetic nuclear resonance (NMR), are intrinsically insensitive to chirality, limiting their application in absolute stereochemistry studies. Historically, chiroptical methods such as optical rotation (OR) and electronic circular dichroism (ECD) has been the techniques of choice for stereochemical studies since they can be applied directly in solution and without requiring either crystallization or derivatizations. OR and ECD are mainly used by means of comparisons of data obtained for structurally related molecules or by the application of empirical rules. The apparent ease of application of chiroptical methods, however, may be deceiving. An increasing number of absolute configuration reassignment has been reported in the literature and many incorrect assignments are due to empirical rule exceptions. Current guidelines for interpretation of chiroptical data involve the quantum chemical simulation of theoretical spectra. Despite recent advances, such simulations are still not routine in natural product chemistry laboratories worldwide. Thus, the present project aims to systematically investigate both the experimental and theoretical chiroptical properties of furan and furofuran type lignans isolated from Aristholochia species in order to verify the applicability as well as limitations of the main empirical correlations/rules found in literature. Additionally, vibrational circular dichroism (VCD) investigations will be carried out. This way, this project will provide validated tools for the correct stereochemical analysis of this important class of secondary metabolites. (AU)

Scientific publications

(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.; SCHOELLHORN, SYDNEY M.; DE S. BARBOSA, CAMILA; MENDES, GIOVANA R.; DE L. MACEDO, KAMILA; FERREIRA, ANTONIO G.; VENANCIO, TIAGO; GUIDO, RAFAEL V. C.; BATISTA, ANDREA N. L.; BATISTA JR, JOAO M.; et al. Structure and Biosynthesis of Perochalasins A-C, Open-Chain Merocytochalasans Produced by the Marine-Derived Fungus Peroneutypa sp. M16. Journal of Natural Products, v. 87, n. 9, p. 12-pg., 2024-08-16. (20/01229-5, 15/01017-0, 19/22319-5, 19/17721-9, 20/12904-5, 23/12475-5, 22/15570-6)

MESTRINER, ELOA R.; LEE, ERIC Y.; CUNHA, CAMILA L.; SOUSA, VICTOR M. S.; NASCIMENTO, ISABELE R.; BATISTA JR, JOAO M.. Resolution and Absolute Configuration of Fargesin Enantiomers. CHIRALITY, v. 36, n. 11, p. 6-pg., 2024-11-01. (23/12475-5)

BATISTA, ANDREA N. L.; VALVERDE, ALESSANDRA L.; NAFIE, LAURENCE A.; BATISTA JR, JOAO M.. Stereochemistry of natural products from vibrational circular dichroism. CHEMICAL COMMUNICATIONS, v. 60, n. 76, p. 12-pg., 2024-08-26. (23/12475-5)