Conformational analysis and electronic interactions of some 2-[2 `-(4 `-sustituted-phenylsulfanyl)-acetyl]-5-substituted furans and 2-[2 `-(phenylselanyl)-acetyl]-5-methylfuran

Author(s)

Valenca, J. ^[1] ; Olivato, Paulo R. ^[1] ; Rodrigues, Daniel N. S. ^[2] ; Batista, Patrick R. ^[3] ; Ducati, Lucas C. ^[3] ; Dal Colle, Maurizio ^[4]

Affiliation

^[1] Univ Sao Paulo, Inst Quim, Conformat Anal & Elect Interact Lab, CP 26077, BR-05513970 Sao Paulo, SP - Brazil

^[2] Univ Fed Sao Paulo UNIFESP, Chem Dept, BR-09972270 Sao Paulo, SP - Brazil

^[3] Univ Sao Paulo, Corse Lab Computat Res Simulat & Spect, Inst Quim, CP 26077, BR-05513970 Sao Paulo, SP - Brazil

^[4] Univ Ferrara, Dipartimento Sci Chim & Farmaceut, I-44121 Ferrara - Italy

• Document type: Journal article
• Source: Journal of Molecular Structure; v. 1225, FEB 5 2021.
• Web of Science Citations: 1

Abstract

The conformational equilibrium of 2-{[}2'-(phenylselanyl)-acetyl]-5-methylfuran (1) and 2-{[}2'-(4'-sustituted-phenylsulfanyl)-acetyl]-5-substituted furans (2'7) was determined through the infrared (IR) analysis of the carbonyl stretching band (nu(CO)) supported by M06'2X/aug-cc-pVDZ level of theory. Three stable conformations {[}sc(anti), ac(anti) and sc(syn)] were obtained in vacuum, with the sc(anti) the most stable for compound 1'6 and the ac(anti) for compound 7. The IR spectrain solution of n-C6H14, CCl4, CHCl3, CH2Cl2 and CH3CN show in general nu(CO) doublets for compounds 2-6, with the exception of triplets in n-C6H14 for 2-4 and a symmetrical band in CHCl3 for 1, 3-6 and in CH2Cl2 and CH3CN for 1. The p-nitrophenyl compound 7 is insoluble in n-C6H14 and CCl4 and displays a doublet in all the other polar solvents. The PCM data allow to ascribe the sc(anti) conformer to the lowest frequency more intense nu(CO) IR component and the sc(syn) one to the other doublet component for compounds 1-6, while the intermediary nu(CO) frequency ac(anti) conformer, with negligible population, is assignedto the third triplet component predicted in n-C6H14 for compounds 2-4. Conversely, for compound 7, the more intense and lowest frequency nu COIR component was ascribed to the ac(anti), whereas the highest frequency one to the sum of the sc(anti) and sc(syn) populations. The conformational preferences of compounds 1-7 are governed by a balance between the orbital and the coulombic interactions estimated by means of natural bond orbitals (NBO), quantum theory of atoms in molecules (QTAIM), non covalent interaction (NCI) and short contacts analysis. While NBO delocalization energies indicate the ac(anti) conformer as the most stable for all compounds, NCI analysis reveals in the sc(anti) and sc(syn) conformers of compounds 1-6 an additional intramolecular stabilizing pi center dot center dot center dot pi stacking interaction between the furyl and phenyl ring, which is counterbalanced in the sc(syn) conformer by the repulsive coulombic short contact between the carbonyl and furyl oxygen atoms. For compound 7, the ac(anti) conformer turns to be the most stable one as the electron withdrawing effect of the nitro substituent on the phenyl ring decreasesthe stabilizing pi center dot center dot center dot pi stacking on the sc(anti) conformer. (C) 2020 Elsevier B.V. All rights reserved. (AU)

• FAPESP's process: 17/17750-3 - Solvent Effect in NMR Parameters by ab initio Molecular Dynamics
• Grantee: Lucas Colucci Ducati
• Support Opportunities: Regular Research Grants
• FAPESP's process: 16/21676-0 - Enantioselective haloamination reactions aiming the synthesis of aminodiols
• Grantee: Alessandro Rodrigues
• Support Opportunities: Regular Research Grants
• FAPESP's process: 18/07308-4 - Effect of solvent on shielding tensor and coupling constant calculations of platinum (iii) dinuclear complexes via ab initio molecular dynamics
• Grantee: Patrick Rodrigues Batista
• Support Opportunities: Scholarships in Brazil - Doctorate