title: Glycosyl-Templated Chiral Helix Stapling of Ethynylpyridine Oligomers by Alkene Metathesis between Inter-Pitch Side Chains.
abstract: Ethynylpyridine polymers and oligomers consisting of 4-substituted pyridine rings linked by acetylene bonds at the 2- and 6-positions have been investigated. Ethynylpyridine oligomers covalently linked with a glycosyl chiral template form chiral helical complexes by intramolecular hydrogen bonding, in which the chirality of the template is translated to the helix. With a view to fixation of the chiral architecture, D/L-galactosyl- and D/L-mannosyl-linked ethynylpyridine oligomers have been developed with 4-(3-butenyloxy)pyridine units having alkene side chains. The helical structures are successfully stapled by alkene metathesis of the side chains. Subsequent removal of the chiral templates by acidolysis produces template-free stapled oligomers. The chiral, template-free, stapled oligomers show chiral helicity, which is resistant to polar solvents and heating.
authors.affiliation: Graduate School of Pharmaceutical Sciences, University of Toyama, Sugitani 2630, Toyama 930-0194 (Japan), Fax: (+81) 76-434-5049. abeh@pha.u-toyama.ac.jp.
authors.forename: Hajime
authors.initials: H
authors.lastname: Abe
authors.affiliation: Graduate School of Pharmaceutical Sciences, University of Toyama, Sugitani 2630, Toyama 930-0194 (Japan), Fax: (+81) 76-434-5049.
authors.forename: Fumihiro
authors.initials: F
authors.lastname: Kayamori
authors.affiliation: Graduate School of Pharmaceutical Sciences, University of Toyama, Sugitani 2630, Toyama 930-0194 (Japan), Fax: (+81) 76-434-5049.
authors.forename: Masahiko
authors.initials: M
authors.lastname: Inouye
mesh_terms: D002942:Circular Dichroism; D006027:Glycosides / Q000138:chemical synthesis* / Q000737:chemistry; D006860:Hydrogen Bonding; D015394:Molecular Structure; D011725:Pyridines / Q000138:chemical synthesis* / Q000737:chemistry*; D012997:Solvents / Q000737:chemistry; D013237:Stereoisomerism
chemical_list: C000605530:4-(3-butenyloxy)pyridine; D006027:Glycosides; D011725:Pyridines; D012997:Solvents; C507758:ethynylpyridine
keywords: chirality; glycosides; helical structures; hydrogen bonds; template synthesis