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Site‐Selective C−H Arylation of Diverse Arenes Ortho to Small Alkyl Groups


Dhankhar, Jyoti; Hofer, Micha D; Linden, Anthony; Coric, Ilija (2022). Site‐Selective C−H Arylation of Diverse Arenes Ortho to Small Alkyl Groups. Angewandte Chemie Internationale Edition, 61(39):e202205470.

Abstract

Catalytic systems for direct C−H activation of arenes commonly show preference for electronically activated and sterically exposed C−H sites. Here we show that a range of functionally rich and pharmaceutically relevant arene classes can undergo site-selective C−H arylation ortho to small alkyl substituents, preferably endocyclic methylene groups. The C−H activation is experimentally supported as being the selectivity-determining step, while computational studies of the transition state models indicate the relevance of non-covalent interactions between the catalyst and the methylene group of the substrate. Our results suggest that preference for C(sp2)−H activation next to alkyl groups could be a general selectivity mode, distinct from common steric and electronic factors.

Abstract

Catalytic systems for direct C−H activation of arenes commonly show preference for electronically activated and sterically exposed C−H sites. Here we show that a range of functionally rich and pharmaceutically relevant arene classes can undergo site-selective C−H arylation ortho to small alkyl substituents, preferably endocyclic methylene groups. The C−H activation is experimentally supported as being the selectivity-determining step, while computational studies of the transition state models indicate the relevance of non-covalent interactions between the catalyst and the methylene group of the substrate. Our results suggest that preference for C(sp2)−H activation next to alkyl groups could be a general selectivity mode, distinct from common steric and electronic factors.

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Additional indexing

Item Type:Journal Article, refereed, original work
Communities & Collections:07 Faculty of Science > Department of Chemistry
Dewey Decimal Classification:540 Chemistry
Scopus Subject Areas:Physical Sciences > Catalysis
Physical Sciences > General Chemistry
Uncontrolled Keywords:General Chemistry, Catalysis
Language:English
Date:26 September 2022
Deposited On:31 Jan 2023 18:40
Last Modified:30 Jan 2024 02:38
Publisher:Wiley-VCH Verlag
ISSN:1433-7851
OA Status:Green
Free access at:PubMed ID. An embargo period may apply.
Publisher DOI:https://doi.org/10.1002/anie.202205470
PubMed ID:35830351
Project Information:
  • : FunderUniversität Zürich
  • : Grant ID
  • : Project Title
  • : FunderHolcim Stiftung zur Förderung der Wissenschaftlichen Fortbildung
  • : Grant ID
  • : Project Title
  • : FunderSNSF
  • : Grant ID206021_16401
  • : Project Title
  • Content: Published Version
  • Language: English
  • Licence: Creative Commons: Attribution-NonCommercial-NoDerivatives 4.0 International (CC BY-NC-ND 4.0)