Theoretical and Experimental Investigations of Circular Dichroism and Absolute Configuration Determination of Chiral Anthracene Photodimers
- 5 March 2012
- journal article
- Published by American Chemical Society (ACS) in Journal of the American Chemical Society
- Vol. 134 (10), 4990-4997
- https://doi.org/10.1021/ja300522y
Abstract
Substituted anthracenes photodimerize to stereoisomeric [4 + 4] cyclodimers, some of which are inherently chiral. Recent supramolecular photochirogenic studies enabled the efficient preparation of specific stereoisomers, the absolute configurations of which should reflect the chiral environment of supramolecular host or scaffold employed but have not been determined, hindering detailed mechanistic elucidation and further host/scaffold design. In this study, we performed the combined experimental and state-of-the-art theoretical analyses of the circular dichroism spectra of chiral cyclodimers of 2-anthracenecarboxylic and 2,6-anthracenedicarboxylic acids to reveal the configurational and molecular orbital origin of the Cotton effects observed, and unambiguously determined the absolute configurations of these chiral cyclodimers. The present results allow us to directly correlate the enantiotopic face-selectivity upon photocyclodimerization with the absolute configuration of the cyclodimer derived therefrom and also to precisely elucidate the chiral arrangement of two cyclodimerizing anthracenes.Keywords
This publication has 53 references indexed in Scilit:
- Products and Mechanism of Acene Dimerization. A Computational StudyJournal of the American Chemical Society, 2011
- An organogel system can control the stereochemical course of anthracene photodimerizationChemical Communications, 2009
- Highly Stereoselective Photocyclodimerization of α-Cyclodextrin-Appended Anthracene Mediated by γ-Cyclodextrin and Cucurbit[8]uril: A Dramatic Steric Effect Operating Outside the Binding SiteJournal of the American Chemical Society, 2008
- Highly Enantiomeric Supramolecular [4 + 4] Photocyclodimerization of 2-Anthracenecarboxylate Mediated by Human Serum AlbuminJournal of the American Chemical Society, 2007
- A Hydrophobic Nanocapsule Controls the Photophysics of Aromatic Molecules by Suppressing Their Favored Solution PathwaysJournal of the American Chemical Society, 2005
- Photochemical Ligation of DNA Conjugates through Anthracene Cyclodimer Formation and Its Fidelity to the Template SequencesJournal of the American Chemical Society, 2004
- Supramolecular Catalysis of the Enantiodifferentiating [4 + 4] Photocyclodimerization of 2-Anthracenecarboxylate by γ-CyclodextrinJournal of the American Chemical Society, 2002
- Photodimerization of anthracenes in fluid solutions: (part 2) mechanistic aspects of the photocycloaddition and of the photochemical and thermal cleavageChemical Society Reviews, 2001
- Photodimerization of anthracenes in fluid solution: structural aspectsChemical Society Reviews, 2000
- Unimolecular photochemistry of anthracenesChemical Reviews, 1993