Controllability of dynamic double helices: quantitative analysis of the inversion of a screw-sense preference upon complexation

• Katoono, Ryo

• Kawai, Shunsuke

• Fujiwara, Kenshu

• Suzuki, Takanori

Abstract

We describe a quantitative analysis of the complexation-induced inversion of a screw-sense preference based on a conformationally dynamic double-helix structure in a macrocycle. The macrocycle is composed of two twisting units (terephthalamide), which are spaced by two strands (1,3-bis(phenylethynyl)benzene), and is designed to generate a double-helix structure through twisting about a C-2 axis in a conrotatory manner. The attachment of chiral auxiliaries to the twisting units induces a helical preference for a particular sense of (M)- or (P)-helicity through the intramolecular transmission of chirality to dynamic double helices. The twisting unit can also act as a binding site for capturing a guest molecule, and, in a complexed state, the preferred screw sense of the dynamic double-helix structure is reversed to exhibit the contrary preference. We quantitatively monitored the complexation-induced inversion of the screw-sense preference using H-1 NMR spectroscopy, which enabled us to observe independently two species with (M)- or (P)-helicity in both the absence and presence of a guest molecule. Inversion of the screw-sense preference was induced upon complexation with an achiral guest as well as a chiral guest.

Journal

• Chemical science

  Chemical science 6 (11), 6592-6600, 2015-12-10

  Royal Society of Chemistry

Keywords

• General Chemistry

Details

• CRID: 1050282813996017024
• NII Article ID: 120005676278
• DOI: 10.1039/c5sc02614h
• ISSN: 20416539
• ISSN: 20416520
• HANDLE: 2115/60296
• Web Site: http://pubs.rsc.org/en/content/articlepdf/2015/SC/C5SC02614H
• Text Lang: en
• Article Type: journal article
• Data Source:
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