Back
Stereochemical significance of O to N atom interchanges within cationic helicenes: experimental and computational evidence of near racemization to remarkable enantiospecificity.
Journal article

Stereochemical significance of O to N atom interchanges within cationic helicenes: experimental and computational evidence of near racemization to remarkable enantiospecificity.

  • Labrador GM Department of Organic Chemistry , University of Geneva , Switzerland . Email: Amalia.PobladorBahamonde@unige.ch ; Email: johann.bosson@unige.ch ; Email: jerome.lacour@unige.ch.
  • Besnard C Laboratory of Crystallography , University of Geneva , Switzerland.
  • Bürgi T Department of Physical Chemistry , University of Geneva , Switzerland.
  • Poblador-Bahamonde AI Department of Organic Chemistry , University of Geneva , Switzerland . Email: Amalia.PobladorBahamonde@unige.ch ; Email: johann.bosson@unige.ch ; Email: jerome.lacour@unige.ch.
  • Bosson J Department of Organic Chemistry , University of Geneva , Switzerland . Email: Amalia.PobladorBahamonde@unige.ch ; Email: johann.bosson@unige.ch ; Email: jerome.lacour@unige.ch.
  • Lacour J Department of Organic Chemistry , University of Geneva , Switzerland . Email: Amalia.PobladorBahamonde@unige.ch ; Email: johann.bosson@unige.ch ; Email: jerome.lacour@unige.ch.
Show more…
  • 2019-10-08
Published in:
  • Chemical science. - 2019
English Oxygen atoms of cationic dioxa and azaoxa [6]helicenes can be exchanged by amino groups to form azaoxa and diaza [6]helicenes respectively. The mild reaction conditions developed herein allow the construction of libraries of derivatives with sensitive and/or functionalized side chains. Using enantioenriched dioxa or azaoxa helicene precursors, these exchanges lead to either near racemization (es 3%) or to a remarkable enantiospecificity (es up to 97%). This unusual behavior is fully characterized via experimental and computational mechanistic evidence. Based on these investigations, the enantiospecificity of the first transformation can be improved to 57-61%.
Language
  • English
Open access status
gold
Identifiers
Persistent URL
https://folia.unifr.ch/global/documents/29391
Statistics
Document views: 16 File downloads: