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Chiral Atropisomeric Indenocorannulene Bowls: Critique of the Cahn-Ingold-Prelog Conception of Molecular Chirality


Wang, Yujia; Allemann, Oliver; Balaban, T Silviu; Vanthuyne, Nicolas; Linden, Anthony; Baldridge, Kim K; Siegel, Jay S (2018). Chiral Atropisomeric Indenocorannulene Bowls: Critique of the Cahn-Ingold-Prelog Conception of Molecular Chirality. Angewandte Chemie Internationale Edition, 57(22):6470-6474.

Abstract

Chiral corannulenes abound, but suffer generally from configurational lability associated with bowl-to-bowl inversion,[1] thus obviating questions of stereogenicity and stereoelement construction.[2] In contrast, peri-annulated corannulenes show greatly increased barriers for bowl-to-bowl inversion; specifically indenocorannulenes invert on a time scale too slow to observe by normal NMR methods and raise the possibility of creating chiral atropisomeric bowl-shaped aromatics.[3] Two methods for preparing indenocorannulene from simple 2-haloarylcorannulenes—silyl cation C–F activation,[ 4] and Pd-mediated C–Cl activation[5]—enable the synthesis of an array of such chiral atropisomeric indenocorannulenes.[ 6] Resolution of the enantiomers by high-performance liquid chromatography over chiral support phases motivates the study of chiroptical properties, the assignment of absolute “Cartesian” configuration, and the assessment of configurational stability.[7] These studies bring into question any systematic assignment of nontrivial stereoelements (i.e. not the molecule in its entirety) and refute any assertion of congruence between “Cahn–Ingold–Prelog elements” and the physical or “Cartesian” basis of chirality

Abstract

Chiral corannulenes abound, but suffer generally from configurational lability associated with bowl-to-bowl inversion,[1] thus obviating questions of stereogenicity and stereoelement construction.[2] In contrast, peri-annulated corannulenes show greatly increased barriers for bowl-to-bowl inversion; specifically indenocorannulenes invert on a time scale too slow to observe by normal NMR methods and raise the possibility of creating chiral atropisomeric bowl-shaped aromatics.[3] Two methods for preparing indenocorannulene from simple 2-haloarylcorannulenes—silyl cation C–F activation,[ 4] and Pd-mediated C–Cl activation[5]—enable the synthesis of an array of such chiral atropisomeric indenocorannulenes.[ 6] Resolution of the enantiomers by high-performance liquid chromatography over chiral support phases motivates the study of chiroptical properties, the assignment of absolute “Cartesian” configuration, and the assessment of configurational stability.[7] These studies bring into question any systematic assignment of nontrivial stereoelements (i.e. not the molecule in its entirety) and refute any assertion of congruence between “Cahn–Ingold–Prelog elements” and the physical or “Cartesian” basis of chirality

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Additional indexing

Item Type:Journal Article, refereed, original work
Communities & Collections:07 Faculty of Science > Department of Chemistry
Dewey Decimal Classification:540 Chemistry
Uncontrolled Keywords:bowl-shaped arenes, Cahn–Ingold–Prelog system, chirality, circular dichroism spectroscopy, indenocorannulenes
Language:English
Date:28 May 2018
Deposited On:22 Nov 2018 08:36
Last Modified:23 Nov 2018 08:31
Publisher:Wiley-VCH Verlag
ISSN:1433-7851
OA Status:Closed
Free access at:Publisher DOI. An embargo period may apply.
Publisher DOI:https://doi.org/10.1002/anie.201801325

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