HUSCAP logo Hokkaido Univ. logo

Hokkaido University Collection of Scholarly and Academic Papers >
Graduate School of Science / Faculty of Science >
Peer-reviewed Journal Articles, etc >

Dynamic helical cyclophanes with two quadruply-bridged planes arranged in an "obverse and/or reverse" relation

This item is licensed under:Creative Commons Attribution 3.0 Unported

Files in This Item:
CS7 3240-3247.pdf1.04 MBPDFView/Open
Please use this identifier to cite or link to this item:

Title: Dynamic helical cyclophanes with two quadruply-bridged planes arranged in an "obverse and/or reverse" relation
Authors: Katoono, Ryo Browse this author
Kawai, Shunsuke Browse this author
Suzuki, Takanori Browse this author
Issue Date: 1-May-2016
Publisher: Royal Society of Chemistry
Journal Title: Chemical science
Volume: 7
Issue: 5
Start Page: 3240
End Page: 3247
Publisher DOI: 10.1039/c5sc04673d
Abstract: We describe the design of two types of cyclophanes that generate dynamic helicity through the twisting of two planes in a clockwise or counterclockwise direction to give (M)- or (P)-helicity. We used a rectangular and anisotropic plane of 1,2,4,5-tetrakis(phenylethynyl) benzene (TPEB), since it can be stacked in pairs in two ways, in parallel or orthogonally, to be identified as distinct cyclophane molecules. We adopted a synthetic strategy for obtaining these two cyclophanes as a mixture using a macrocyclic intermediate that possessed two rotatable phenyl rings. We introduced necessary parts into the rotators to give a mixture of rotational isomers leading to a parallel or orthogonal arrangement of TPEBs, and then doubly bridged two planes of TPEB to form quadruply-bridged cyclophanes. We consider that such two planes in each cyclophane are in an "obverse and/or reverse" relation. In each cyclophane, we found unique dynamic helical forms with (M)- or (P)-helicity as well as an inherently non-chiral form. Normally, the screw-sense preference of dynamic helicity would be controlled through the intramolecular or supramolecular transmission of central chirality, when a chiral auxiliary is attached to the cyclophanes or a chiral guest is allowed to form a complex with the cyclophanes. In a case where two different substitution groups were used on bridging units to generate planar chirality in each cyclophane, the screw-sense preference was controlled through the arrangement of these substitution groups, and did not depend on the transmission of central chirality. Two different substitution groups desymmetrize the enantiomeric forms with (M)- or (P)-helicity generated in each dynamic helical cyclophane so that two dynamic helical forms with (M)- or (P)-helicity can be in a diastereomeric relation. Thus, a particular screw sense of dynamic helicity can be preferred, regardless of whether or not the two substitution groups possess some chiral element.
Type: article
Appears in Collections:理学院・理学研究院 (Graduate School of Science / Faculty of Science) > 雑誌発表論文等 (Peer-reviewed Journal Articles, etc)

Submitter: 上遠野 亮

Export metadata:

OAI-PMH ( junii2 , jpcoar_1.0 )

MathJax is now OFF:


 - Hokkaido University