Importance of molecular symmetry for enantiomeric excess recognition by NMR. Issue 35 (13th April 2022)

• Record Type: Journal Article
• Authors: Norvaiša, Karolis; O'Brien, John E.; Osadchuk, Irina; Twamley, Brendan; Borovkov, Victor; Senge, Mathias O.
• Is Part Of: Chemical communications. Volume 58:Issue 35(2022)
• Page Start: 5423
• Page End: 5426
• Publication Date: 2022-04-13
• Subjects: Chemistry -- Periodicals; 540
• DOI: 10.1039/d2cc01319c
• Languages: English
• ISSNs: 1359-7345

Abstract

Abstract : Porphyrins with an exposed inner core N–H system respond to a chiral guest with exceptionally sensitive enantiomeric excess detection. Abstract : Recently prochiral solvating agents ( pro -CSA) came under the spotlight for the detection of enantiopurity by NMR. Chemical shift non-equivalency in achiral hosts introduced by the presence of chiral guests yields observable resonance signal splitting (Δ δ ) correlating to the enantiomeric excess (e.e.). In this work, symmetry is our lens to explain porphyrin-based supramolecular receptor activity in a chiral environment. Based on extensive NMR analyses of the atropisomeric receptors, the host symmetry is shown to be affected by porphyrin nonplanarity and further desymmetrized in the presence of a chiral guest. As such, the exposed porphyrin inner core (N–H), with its strong hydrogen bond abilities, for the first time, has been exploited in enantiomeric composition analysis. Our approach in e.e. detection by N–H signals appearing in a previously underutilized region of the spectrum (below 0 ppm) shows chemical shift splitting (Δ δ ) three times more sensitive to enantiomeric compositions than previously reported systems.