Chemistry. 2005 Mar 04;11(6):1877-88. doi: 10.1002/chem.200401002.

Direct assignment of enantiofacial discrimination on single heterocyclic substrates by self-induced CD.

Chemistry (Weinheim an der Bergstrasse, Germany)

Carsten Siering, Stefan Grimme, Siegfried R Waldvogel

PMID: 15674980 DOI: 10.1002/chem.200401002

Abstract

The first direct assignment of highly dynamic enantiofacial discrimination acting on a single heterocyclic substrate has been achieved by a combination of experimental and theoretical CD spectroscopy. The interaction of chirally modified hosts based on triphenylene ketals with appropriate prochiral guests can lead to the preferential formation of one diastereomeric host-guest complex. This reversible stereoselective binding transmits the chiral information from remote chiral groups in the host to the strongly absorbing triphenylene chromophore, which gives rise to self-induced CD. This effect was exploited for the determination of the enantiofacial recognition in various host-guest systems. Inversion of the steric demand either of the chiral substituents at the host or of the prochiral guest leads to almost complete inversion of the resulting CD spectra. For the assignment of the absolute stereochemistry of the complexes, a combined molecular dynamics/quantum-chemical approach was successfully employed. Despite the size and the highly dynamic character of the supramolecular systems, fundamental properties of the systems and details of the spectra were simulated accurately, providing access to fast and reliable assignment of the enantiofacial preference. The results are highly consistent with available X-ray data.

Publication Types

• Journal Article