Full Control of the Chiral Overpass Effect in Helical Polymers: P/M Screw Sense Induction by Remote Chiral Centers After Bypassing the First Chiral Residue

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  • Rafael Rodríguez
    Centro Singular de investigación en Química Biolóxica e Materiais Moleculares (CiQUS) e Departamento de Química Orgánica Universidade de Santiago de Compostela 15782 Santiago de Compostela Spain
  • Elena Rivadulla‐Cendal
    Centro Singular de investigación en Química Biolóxica e Materiais Moleculares (CiQUS) e Departamento de Química Orgánica Universidade de Santiago de Compostela 15782 Santiago de Compostela Spain
  • Manuel Fernández‐Míguez
    Centro Singular de investigación en Química Biolóxica e Materiais Moleculares (CiQUS) e Departamento de Química Orgánica Universidade de Santiago de Compostela 15782 Santiago de Compostela Spain
  • Berta Fernández
    Departamento de Química Física Universidade de Santiago de Compostela 15782 Santiago de Compostela Spain
  • Katsuhiro Maeda
    WPI Nano Life Science Institute (WPI-NanoLSI) Kanazawa University Kakuma-machi Kanazawa 920-1192 Japan
  • Emilio Quiñoá
    Centro Singular de investigación en Química Biolóxica e Materiais Moleculares (CiQUS) e Departamento de Química Orgánica Universidade de Santiago de Compostela 15782 Santiago de Compostela Spain
  • Félix Freire
    Centro Singular de investigación en Química Biolóxica e Materiais Moleculares (CiQUS) e Departamento de Química Orgánica Universidade de Santiago de Compostela 15782 Santiago de Compostela Spain

書誌事項

公開日
2022-10-13
資源種別
journal article
権利情報
  • http://creativecommons.org/licenses/by-nc/4.0/
DOI
  • 10.1002/anie.202209953
  • 10.1002/ange.202209953
公開者
Wiley

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説明

<jats:title>Abstract</jats:title><jats:p>In helical polymers, helical sense induction is usually commanded by teleinduction mechanism, where the largest substituent of the chiral residue directly attached to the main chain is the one that commands the helical sense. In this work, different helical structures with different helical senses are induced in a helical polymer [poly‐(phenylacetylene)] when the conformational composition of two different dihedral angles of a pendant group with more than two chiral residues is tamed. Thus, while the dihedral angle at chiral residue<jats:bold>1</jats:bold>[(<jats:italic>R</jats:italic>)‐ or (<jats:italic>S</jats:italic>)‐alanine], attached to the backbone, produces an extended or bent conformation in the pendant resulting in two scaffolds with different stretching degree, the second dihedral angle at chiral residue<jats:bold>2</jats:bold>[(<jats:italic>R</jats:italic>)‐ or (<jats:italic>S</jats:italic>)‐methoxyphenylacetamide] places the substituents of this chiral center in a different spatial orientation, originating opposite helical senses at the polymer that are induced through a total control of the “chiral overpass effect”.</jats:p>

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