Spectroscopic investigation on 1,2-substituted ferrocenes with only planar chirality: How chiroptical data are related to absolute configuration and to substituents

Year: 2022

Authors: Mazzeo G., Pedotti S., Longhi G., Patti A., Abbate S.

Autors Affiliation: Univ Brescia, Dipartimento Med Mol & Traslaz DMMT, Viale Europa 11, I-25123 Brescia, Italy; Inst Biomol Chem, CNR, Via Paolo Gaifami 18, I-95126 Catania, Italy; INO, CNR, Sede Secondaria Brescia, Via Branze 45, I-25123 Brescia, Italy.

Abstract: Single enantiomers of three 1,2-substituted ferrocene derivatives, i.e. 1-methoxymethyl-2-hydroxyme thylferrocene (1), 1-formyl-2-hydroxymethylferrocene (2) and 1-iodo-2-hydroxymethylferrocene (3), sharing the common hydroxymethyl substituent and the presence of planar chirality only, were investigated for their spectroscopic (IR and UV) and chiroptical (VCD and ECD) properties. Both enantiomers of 1 were obtained for the first time in optically pure form by lipase-catalyzed kinetic resolution of the corresponding racemate (+/-)-1 and separately converted into formyl derivatives (+)-2 and (-)-2.& nbsp;The experimental spectroscopic and chiroptical data were compared with DFT calculated spectra and excellent correspondence was found for all compounds, allowing one to confirm the previously assigned absolute configurations. The common features in the VCD spectra of a doublet between 940 and 965 cm’1 and the short-wavelength (about 200 nm) doublet and the longest wavelength band in the ECD spectra were analyzed to test whether they may be taken as markers of the absolute configuration (AC). The predominance of conformers with intramolecular hydrogen bond for the first two investigated compounds is predicted by conformational analysis and also confirmed by NMR.(c) 2022 Elsevier B.V. All rights reserved.

Journal/Review: SPECTROCHIMICA ACTA PART A-MOLECULAR AND BIOMOLECULAR SPECTROSCOPY

Volume: 272      Pages from: 121010-1  to: 121010-11

More Information: This research has been carried out with the support of resources of Big&Open Data Innovation Laboratory (BODaI-Lab) , University of Brescia, granted by Fondazione Cariplo and Regione Lombardia and of Computing Center CINECA (Bologna) , Italy. Funding from the Italian Ministry of Education, University and Research (MIUR) through the PRIN 2017 program (Project 2017A4XRCA_003 Physico-chemical Heuristic Approaches: Nanoscale Theory of Molecular Spectroscopy [PHANTOMS] ) is acknowledged.
KeyWords: Ferrocenes; Planar Chirality; Lipase-catalyzed resolution; VCD and ECD spectroscopies; Hydrogen Bonding (HB); Density Functional Theory (DFT) calculations
DOI: 10.1016/j.saa.2022.121010

Citations: 2
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