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Dynamic Figure Eight Chirality: Multifarious Inversions of a Helical Preference Induced by Complexation.

Dynamic Figure Eight Chirality: Multifarious Inversions of a Helical Preference Induced by Complexation.

Authors :
Ryo Katoono
Yuki Tanaka
Keiichi Kusaka
Kenshu Fujiwara
Takanori Suzuki
Source :
Journal of Organic Chemistry. 8/7/2015, Vol. 80 Issue 15, p7613-7625. 13p.
Publication Year :
2015

Abstract

We demonstrate two types of inversion of a helical preference upon the 1:1 complexation of a dynamic figure eight molecule with a guest molecule through the controlled transmission of point chirality. We designed a series of macrocycles that prefer a nonplanar conformation with figure eight chirality. These macrocycles are composed of a chirality-transferring unit (terephthalamide) and a structure-modifying unit (two o-phenylene rings spaced with a varying number of triple bonds). The former unit provides a binding site for capturing a guest molecule through the formation of hydrogen bonds. The attachment of chiral auxiliaries to the former unit induces a helical preference for a particular sense through the intramolecular transmission of point chirality. For relatively small-sized macrocycles, the preferred sense was reversed upon complexation with an achiral guest. Contrary preferences before and after complexation were both seen for chiral auxiliaries associated with a figure eight host through two-way intramolecular transmission of the single chiral source. Alternatively, the helical preference induced in relatively large-sized macrocycles was reversed only when a figure eight host formed a 1:1 complex with a particular enantiomeric guest through the supramolecular transmission of point chirality in the guest. This stereospecific inversion of a helical preference is rare. [ABSTRACT FROM AUTHOR]

Details

Language :
English
ISSN :
00223263
Volume :
80
Issue :
15
Database :
Academic Search Index
Journal :
Journal of Organic Chemistry
Publication Type :
Academic Journal
Accession number :
109011892
Full Text :
https://doi.org/10.1021/acs.joc.5b01206