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

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 enantio...

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Autores principales: Labrador, Geraldine M., Besnard, Céline, Bürgi, Thomas, Poblador-Bahamonde, Amalia I., Bosson, Johann, Lacour, Jérôme
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Royal Society of Chemistry 2019
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6676467/
https://www.ncbi.nlm.nih.gov/pubmed/31588273
http://dx.doi.org/10.1039/c9sc02127b
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author Labrador, Geraldine M.
Besnard, Céline
Bürgi, Thomas
Poblador-Bahamonde, Amalia I.
Bosson, Johann
Lacour, Jérôme
author_facet Labrador, Geraldine M.
Besnard, Céline
Bürgi, Thomas
Poblador-Bahamonde, Amalia I.
Bosson, Johann
Lacour, Jérôme
author_sort Labrador, Geraldine M.
collection PubMed
description 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%.
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spelling pubmed-66764672019-10-04 Stereochemical significance of O to N atom interchanges within cationic helicenes: experimental and computational evidence of near racemization to remarkable enantiospecificity Labrador, Geraldine M. Besnard, Céline Bürgi, Thomas Poblador-Bahamonde, Amalia I. Bosson, Johann Lacour, Jérôme Chem Sci Chemistry 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%. Royal Society of Chemistry 2019-06-18 /pmc/articles/PMC6676467/ /pubmed/31588273 http://dx.doi.org/10.1039/c9sc02127b Text en This journal is © The Royal Society of Chemistry 2019 http://creativecommons.org/licenses/by/3.0/ This article is freely available. This article is licensed under a Creative Commons Attribution 3.0 Unported Licence (CC BY 3.0)
spellingShingle Chemistry
Labrador, Geraldine M.
Besnard, Céline
Bürgi, Thomas
Poblador-Bahamonde, Amalia I.
Bosson, Johann
Lacour, Jérôme
Stereochemical significance of O to N atom interchanges within cationic helicenes: experimental and computational evidence of near racemization to remarkable enantiospecificity
title Stereochemical significance of O to N atom interchanges within cationic helicenes: experimental and computational evidence of near racemization to remarkable enantiospecificity
title_full Stereochemical significance of O to N atom interchanges within cationic helicenes: experimental and computational evidence of near racemization to remarkable enantiospecificity
title_fullStr Stereochemical significance of O to N atom interchanges within cationic helicenes: experimental and computational evidence of near racemization to remarkable enantiospecificity
title_full_unstemmed Stereochemical significance of O to N atom interchanges within cationic helicenes: experimental and computational evidence of near racemization to remarkable enantiospecificity
title_short Stereochemical significance of O to N atom interchanges within cationic helicenes: experimental and computational evidence of near racemization to remarkable enantiospecificity
title_sort stereochemical significance of o to n atom interchanges within cationic helicenes: experimental and computational evidence of near racemization to remarkable enantiospecificity
topic Chemistry
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6676467/
https://www.ncbi.nlm.nih.gov/pubmed/31588273
http://dx.doi.org/10.1039/c9sc02127b
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