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Carbene-Controlled Regioselective Functionalization of Linear Alkanes under Silver Catalysis

[Image: see text] Control of the regioselectivity in the functionalization of C–H bonds of linear alkanes C(2)H(2n+2) via carbene transfer from diazo compounds is restricted to the use of rhodium-based catalysts, which govern the reaction outcome employing donor–acceptor diazo reagents. At variance...

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Autores principales: Álvarez, María, Molina, Francisco, Pérez, Pedro J.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2022
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9801380/
https://www.ncbi.nlm.nih.gov/pubmed/36512728
http://dx.doi.org/10.1021/jacs.2c11707
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author Álvarez, María
Molina, Francisco
Pérez, Pedro J.
author_facet Álvarez, María
Molina, Francisco
Pérez, Pedro J.
author_sort Álvarez, María
collection PubMed
description [Image: see text] Control of the regioselectivity in the functionalization of C–H bonds of linear alkanes C(2)H(2n+2) via carbene transfer from diazo compounds is restricted to the use of rhodium-based catalysts, which govern the reaction outcome employing donor–acceptor diazo reagents. At variance with that catalyst-controlled strategy, we present an alternative approach in which employing the appropriate silver complexes containing trispyrazolylborate ligands as catalysts with large differences in their steric and electronic properties, the regioselection is mainly governed by the diazo reagent, which leads to the functionalization of primary or secondary sites of linear alkanes (lacking any activating or directing groups). Donor–acceptor aryl diazoacetates exclusively provide the functionalization of the secondary sites of hexane or pentane, whereas acceptor ethyl diazoacetate leads to an unprecedented level of primary functionalization.
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spelling pubmed-98013802022-12-31 Carbene-Controlled Regioselective Functionalization of Linear Alkanes under Silver Catalysis Álvarez, María Molina, Francisco Pérez, Pedro J. J Am Chem Soc [Image: see text] Control of the regioselectivity in the functionalization of C–H bonds of linear alkanes C(2)H(2n+2) via carbene transfer from diazo compounds is restricted to the use of rhodium-based catalysts, which govern the reaction outcome employing donor–acceptor diazo reagents. At variance with that catalyst-controlled strategy, we present an alternative approach in which employing the appropriate silver complexes containing trispyrazolylborate ligands as catalysts with large differences in their steric and electronic properties, the regioselection is mainly governed by the diazo reagent, which leads to the functionalization of primary or secondary sites of linear alkanes (lacking any activating or directing groups). Donor–acceptor aryl diazoacetates exclusively provide the functionalization of the secondary sites of hexane or pentane, whereas acceptor ethyl diazoacetate leads to an unprecedented level of primary functionalization. American Chemical Society 2022-12-13 2022-12-28 /pmc/articles/PMC9801380/ /pubmed/36512728 http://dx.doi.org/10.1021/jacs.2c11707 Text en © 2022 American Chemical Society https://creativecommons.org/licenses/by/4.0/Permits the broadest form of re-use including for commercial purposes, provided that author attribution and integrity are maintained (https://creativecommons.org/licenses/by/4.0/).
spellingShingle Álvarez, María
Molina, Francisco
Pérez, Pedro J.
Carbene-Controlled Regioselective Functionalization of Linear Alkanes under Silver Catalysis
title Carbene-Controlled Regioselective Functionalization of Linear Alkanes under Silver Catalysis
title_full Carbene-Controlled Regioselective Functionalization of Linear Alkanes under Silver Catalysis
title_fullStr Carbene-Controlled Regioselective Functionalization of Linear Alkanes under Silver Catalysis
title_full_unstemmed Carbene-Controlled Regioselective Functionalization of Linear Alkanes under Silver Catalysis
title_short Carbene-Controlled Regioselective Functionalization of Linear Alkanes under Silver Catalysis
title_sort carbene-controlled regioselective functionalization of linear alkanes under silver catalysis
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9801380/
https://www.ncbi.nlm.nih.gov/pubmed/36512728
http://dx.doi.org/10.1021/jacs.2c11707
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