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Chiral Atropisomeric Indenocorannulene Bowls: Critique of the Cahn–Ingold–Prelog Conception of Molecular Chirality
Author(s) -
Wang Yujia,
Allemann Oliver,
Balaban T. Silviu,
Vanthuyne Nicolas,
Linden Anthony,
Baldridge Kim K.,
Siegel Jay S.
Publication year - 2018
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201801325
Subject(s) - enantiomer , lability , chirality (physics) , assertion , chemistry , stereochemistry , physics , organic chemistry , computer science , chiral symmetry , quantum mechanics , nambu–jona lasinio model , programming language , quark
Chiral corannulenes abound, but suffer generally from configurational lability associated with bowl‐to‐bowl inversion,[1][Y.-T. Wu, 2006] thus obviating questions of stereogenicity and stereoelement construction.[2][K. Mislow, 1984] 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][T. J. Seiders, 2001] Two methods for preparing indenocorannulene from simple 2‐haloarylcorannulenes—silyl cation C–F activation,[4][O. Allemann, 2011] 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.[9][, ] 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.