Selective Nuclear Magnetic Resonance Experiments for Sign-Sensitive Determination of Heteronuclear Couplings: Expanding the Analysis of Crude Reaction Mixtures

Author(s)

Dal Poggetto, Guilherme ^[1] ; Soares, Joao Vitor ^[1] ; Tormena, Claudio F. ^[1]

Affiliation

^[1] Univ Estadual Campinas, Inst Chem, UNICAMP, BR-13083970 Campinas, SP - Brazil

• Document type: Journal article
• Source: Analytical Chemistry; v. 92, n. 20, p. 14047-14053, OCT 20 2020.
• Web of Science Citations: 0

Abstract

State-of-the-art nuclear magnetic resonance (NMR) selective experiments are capable of directly analyzing crude reaction mixtures. A new experiment named HD-HAPPY-FESTA yields ultrahigh-resolution total correlation subspectra, which are suitable for sign-sensitive determination of heteronuclear couplings, as demonstrated here by measuring the sign and magnitude for proton-fluorine couplings (J(HF)) from major and minor isomer products of a two-step reaction without any purification. Proton - fluorine couplings ranging from 51.5 to -2.6 Hz could be measured using HD-HAPPY-FESTA, with the smallest measured magnitude of 0.8 Hz. Experimental J(HF) values were used to identify the two fluoroketone intermediates and the four fluoroalcohol products. Results were rationalized and compared with the density functional theory (DFT) calculations. Experimental data were further compared with the couplings reported in the literature, where pure samples were analyzed. (AU)

• FAPESP's process: 18/19253-0 - NEW PULSE SEQUENCES AND PROCESSING TOOLS FOR MULTIDIMENSIONAL NMR EXPERIMENTS APPLIED TO NATURAL PRODUCTS MIXTURE ANALYSIS
• Grantee: Guilherme Fonseca Dal Poggetto
• Support Opportunities: Scholarships in Brazil - Post-Doctoral
• FAPESP's process: 15/08541-6 - Nuclear magnetic resonance spectroscopy: beyond molecular structure assignment
• Grantee: Claudio Francisco Tormena
• Support Opportunities: Research Projects - Thematic Grants