In-Fjord Substitution in Expanded Helicenes: Effects of the Insert on the Inversion Barrier and Helical Pitch.
Au catalysis
expanded helicenes
hydroarylation
polycyclic aromatic compounds
racemization barriers
Journal
Chemistry (Weinheim an der Bergstrasse, Germany)
ISSN: 1521-3765
Titre abrégé: Chemistry
Pays: Germany
ID NLM: 9513783
Informations de publication
Date de publication:
20 Sep 2021
20 Sep 2021
Historique:
received:
16
07
2021
pubmed:
22
7
2021
medline:
22
9
2021
entrez:
21
7
2021
Statut:
ppublish
Résumé
A series of expanded helicenes of different sizes and shapes incorporating phenyl- and biphenyl-substituents at the deepest part of their fjord have been synthesized via sequential Au-catalyzed hydroarylation of appropriately designed diynes, and their racemization barriers have been calculated employing electronic structure methods. These show that the overall profile of the inversions (energies, number of transition states and intermediates, and their relative position) is intensively affected by the interplay of steric and attractive London dispersion interactions. Hence, in-fjord substitution constitutes an additional tool to handle the mechanical properties in helicenes of uncommonly large diameter. The photochemical characterization of the newly prepared helical structures is also reported.
Identifiants
pubmed: 34288171
doi: 10.1002/chem.202102585
pmc: PMC8519012
doi:
Substances chimiques
Polycyclic Compounds
0
helicenes
0
Types de publication
Journal Article
Langues
eng
Sous-ensembles de citation
IM
Pagination
13358-13366Subventions
Organisme : deutsche forschungsgemeinschaft
ID : Al 1348/4-3
Organisme : deutsche forschungsgemeinschaft
ID : INST 186/1237-1
Organisme : deutsche forschungsgemeinschaft
ID : INST 186/1298-1
Organisme : deutsche forschungsgemeinschaft
ID : GKR 2455
Informations de copyright
© 2021 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.
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