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Copper‐Catalyzed Borylation of Acyl Chlorides with an Alkoxy Diboron Reagent: A Facile Route to Acylboron Compounds

Herein, the copper‐catalyzed borylation of readily available acyl chlorides with bis(pinacolato)diboron, (B(2)pin(2)) or bis(neopentane glycolato)diboron (B(2)neop(2)) is reported, which provides stable potassium acyltrifluoroborates (KATs) in good yields from the acylboronate esters. A variety of f...

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Autores principales: Zhang, Xiaolei, Friedrich, Alexandra, Marder, Todd B.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: John Wiley and Sons Inc. 2022
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9400893/
https://www.ncbi.nlm.nih.gov/pubmed/35510606
http://dx.doi.org/10.1002/chem.202201329
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author Zhang, Xiaolei
Friedrich, Alexandra
Marder, Todd B.
author_facet Zhang, Xiaolei
Friedrich, Alexandra
Marder, Todd B.
author_sort Zhang, Xiaolei
collection PubMed
description Herein, the copper‐catalyzed borylation of readily available acyl chlorides with bis(pinacolato)diboron, (B(2)pin(2)) or bis(neopentane glycolato)diboron (B(2)neop(2)) is reported, which provides stable potassium acyltrifluoroborates (KATs) in good yields from the acylboronate esters. A variety of functional groups are tolerated under the mild reaction conditions (room temperature) and substrates containing different carbon‐skeletons, such as aryl, heteroaryl and primary, secondary, tertiary alkyl are applicable. Acyl N‐methyliminodiacetic acid (MIDA) boronates can also been accessed by modification of the workup procedures. This process is scalable and also amenable to the late‐stage conversion of carboxylic acid‐containing drugs into their acylboron analogues, which have been challenging to prepare previously. A catalytic mechanism is proposed based on in situ monitoring of the reaction between p‐toluoyl chloride and an NHC‐copper(I) boryl complex as well as the isolation of an unusual lithium acylBpinOBpin compound as a key intermediate.
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spelling pubmed-94008932022-08-26 Copper‐Catalyzed Borylation of Acyl Chlorides with an Alkoxy Diboron Reagent: A Facile Route to Acylboron Compounds Zhang, Xiaolei Friedrich, Alexandra Marder, Todd B. Chemistry Research Articles Herein, the copper‐catalyzed borylation of readily available acyl chlorides with bis(pinacolato)diboron, (B(2)pin(2)) or bis(neopentane glycolato)diboron (B(2)neop(2)) is reported, which provides stable potassium acyltrifluoroborates (KATs) in good yields from the acylboronate esters. A variety of functional groups are tolerated under the mild reaction conditions (room temperature) and substrates containing different carbon‐skeletons, such as aryl, heteroaryl and primary, secondary, tertiary alkyl are applicable. Acyl N‐methyliminodiacetic acid (MIDA) boronates can also been accessed by modification of the workup procedures. This process is scalable and also amenable to the late‐stage conversion of carboxylic acid‐containing drugs into their acylboron analogues, which have been challenging to prepare previously. A catalytic mechanism is proposed based on in situ monitoring of the reaction between p‐toluoyl chloride and an NHC‐copper(I) boryl complex as well as the isolation of an unusual lithium acylBpinOBpin compound as a key intermediate. John Wiley and Sons Inc. 2022-06-13 2022-07-26 /pmc/articles/PMC9400893/ /pubmed/35510606 http://dx.doi.org/10.1002/chem.202201329 Text en © 2022 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH https://creativecommons.org/licenses/by/4.0/This is an open access article under the terms of the http://creativecommons.org/licenses/by/4.0/ (https://creativecommons.org/licenses/by/4.0/) License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.
spellingShingle Research Articles
Zhang, Xiaolei
Friedrich, Alexandra
Marder, Todd B.
Copper‐Catalyzed Borylation of Acyl Chlorides with an Alkoxy Diboron Reagent: A Facile Route to Acylboron Compounds
title Copper‐Catalyzed Borylation of Acyl Chlorides with an Alkoxy Diboron Reagent: A Facile Route to Acylboron Compounds
title_full Copper‐Catalyzed Borylation of Acyl Chlorides with an Alkoxy Diboron Reagent: A Facile Route to Acylboron Compounds
title_fullStr Copper‐Catalyzed Borylation of Acyl Chlorides with an Alkoxy Diboron Reagent: A Facile Route to Acylboron Compounds
title_full_unstemmed Copper‐Catalyzed Borylation of Acyl Chlorides with an Alkoxy Diboron Reagent: A Facile Route to Acylboron Compounds
title_short Copper‐Catalyzed Borylation of Acyl Chlorides with an Alkoxy Diboron Reagent: A Facile Route to Acylboron Compounds
title_sort copper‐catalyzed borylation of acyl chlorides with an alkoxy diboron reagent: a facile route to acylboron compounds
topic Research Articles
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9400893/
https://www.ncbi.nlm.nih.gov/pubmed/35510606
http://dx.doi.org/10.1002/chem.202201329
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AT mardertoddb coppercatalyzedborylationofacylchlorideswithanalkoxydiboronreagentafacileroutetoacylboroncompounds