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Modular preparation of cationic bipyridines and azaarenes via C–H activation

Bipyridines are ubiquitous in organic and inorganic chemistry because of their redox and photochemical properties and their utility as ligands to transition metals. Cationic substituents on bipyridines and azaarenes are valuable as powerful electron-withdrawing functionalities that also enhance solu...

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Autores principales: King, Ryan P., Yang, Jenny Y.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: The Royal Society of Chemistry 2023
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10686024/
https://www.ncbi.nlm.nih.gov/pubmed/38033896
http://dx.doi.org/10.1039/d3sc04864k
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author King, Ryan P.
Yang, Jenny Y.
author_facet King, Ryan P.
Yang, Jenny Y.
author_sort King, Ryan P.
collection PubMed
description Bipyridines are ubiquitous in organic and inorganic chemistry because of their redox and photochemical properties and their utility as ligands to transition metals. Cationic substituents on bipyridines and azaarenes are valuable as powerful electron-withdrawing functionalities that also enhance solubility in polar solvents, but there are no general methods for direct functionalization. A versatile method for the preparation of trimethylammonium- and triarylphosphonium-substituted bipyridines and azaheterocycles is disclosed. This methodology showcases a C–H activation of pyridine N-oxides that enables a highly modular and scalable synthesis of a diverse array of cationically charged azaarenes. The addition of trimethylammonium functionalities on bipyridine derivatives resulted in more anodic reduction potentials (up to 700 mV) and increased electrochemical reversibility compared to the neutral unfunctionalized bipyridine. Additonally, metallation of 4-triphenylphosphinated biquinoline to make the corresponding Re(CO)(3)Cl complex resulted in reduction potentials 400 mV more anodic than the neutral derivative.
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spelling pubmed-106860242023-11-30 Modular preparation of cationic bipyridines and azaarenes via C–H activation King, Ryan P. Yang, Jenny Y. Chem Sci Chemistry Bipyridines are ubiquitous in organic and inorganic chemistry because of their redox and photochemical properties and their utility as ligands to transition metals. Cationic substituents on bipyridines and azaarenes are valuable as powerful electron-withdrawing functionalities that also enhance solubility in polar solvents, but there are no general methods for direct functionalization. A versatile method for the preparation of trimethylammonium- and triarylphosphonium-substituted bipyridines and azaheterocycles is disclosed. This methodology showcases a C–H activation of pyridine N-oxides that enables a highly modular and scalable synthesis of a diverse array of cationically charged azaarenes. The addition of trimethylammonium functionalities on bipyridine derivatives resulted in more anodic reduction potentials (up to 700 mV) and increased electrochemical reversibility compared to the neutral unfunctionalized bipyridine. Additonally, metallation of 4-triphenylphosphinated biquinoline to make the corresponding Re(CO)(3)Cl complex resulted in reduction potentials 400 mV more anodic than the neutral derivative. The Royal Society of Chemistry 2023-11-15 /pmc/articles/PMC10686024/ /pubmed/38033896 http://dx.doi.org/10.1039/d3sc04864k Text en This journal is © The Royal Society of Chemistry https://creativecommons.org/licenses/by/3.0/
spellingShingle Chemistry
King, Ryan P.
Yang, Jenny Y.
Modular preparation of cationic bipyridines and azaarenes via C–H activation
title Modular preparation of cationic bipyridines and azaarenes via C–H activation
title_full Modular preparation of cationic bipyridines and azaarenes via C–H activation
title_fullStr Modular preparation of cationic bipyridines and azaarenes via C–H activation
title_full_unstemmed Modular preparation of cationic bipyridines and azaarenes via C–H activation
title_short Modular preparation of cationic bipyridines and azaarenes via C–H activation
title_sort modular preparation of cationic bipyridines and azaarenes via c–h activation
topic Chemistry
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10686024/
https://www.ncbi.nlm.nih.gov/pubmed/38033896
http://dx.doi.org/10.1039/d3sc04864k
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