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Pd-catalyzed intramolecular addition of active methylene compounds to alkynes with subsequent cross-coupling with (hetero)aryl halides

We report an efficient protocol for tandem Pd-catalyzed intramolecular addition of active methylene compounds to alkynes, followed by subsequent cross-coupling with (hetero)aryl bromides and chlorides. The reaction proceeds under mild conditions, providing excellent functional group tolerance, inclu...

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Autores principales: Błocka, Aleksandra, Woźnicki, Paweł, Stankevič, Marek, Chaładaj, Wojciech
Formato: Online Artículo Texto
Lenguaje:English
Publicado: The Royal Society of Chemistry 2019
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9076196/
https://www.ncbi.nlm.nih.gov/pubmed/35541417
http://dx.doi.org/10.1039/c9ra08002c
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author Błocka, Aleksandra
Woźnicki, Paweł
Stankevič, Marek
Chaładaj, Wojciech
author_facet Błocka, Aleksandra
Woźnicki, Paweł
Stankevič, Marek
Chaładaj, Wojciech
author_sort Błocka, Aleksandra
collection PubMed
description We report an efficient protocol for tandem Pd-catalyzed intramolecular addition of active methylene compounds to alkynes, followed by subsequent cross-coupling with (hetero)aryl bromides and chlorides. The reaction proceeds under mild conditions, providing excellent functional group tolerance, including unprotected OH, NH(2) groups, enolizable ketones, or a variety of heterocycles. Mechanistic studies point towards a catalytic cycle involving oxidative addition, intramolecular nucleophilic addition to the Pd(ii)-activated alkyne, and reductive elimination, with 5-exo-dig cyclization being the rate limiting step.
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spelling pubmed-90761962022-05-09 Pd-catalyzed intramolecular addition of active methylene compounds to alkynes with subsequent cross-coupling with (hetero)aryl halides Błocka, Aleksandra Woźnicki, Paweł Stankevič, Marek Chaładaj, Wojciech RSC Adv Chemistry We report an efficient protocol for tandem Pd-catalyzed intramolecular addition of active methylene compounds to alkynes, followed by subsequent cross-coupling with (hetero)aryl bromides and chlorides. The reaction proceeds under mild conditions, providing excellent functional group tolerance, including unprotected OH, NH(2) groups, enolizable ketones, or a variety of heterocycles. Mechanistic studies point towards a catalytic cycle involving oxidative addition, intramolecular nucleophilic addition to the Pd(ii)-activated alkyne, and reductive elimination, with 5-exo-dig cyclization being the rate limiting step. The Royal Society of Chemistry 2019-12-03 /pmc/articles/PMC9076196/ /pubmed/35541417 http://dx.doi.org/10.1039/c9ra08002c Text en This journal is © The Royal Society of Chemistry https://creativecommons.org/licenses/by/3.0/
spellingShingle Chemistry
Błocka, Aleksandra
Woźnicki, Paweł
Stankevič, Marek
Chaładaj, Wojciech
Pd-catalyzed intramolecular addition of active methylene compounds to alkynes with subsequent cross-coupling with (hetero)aryl halides
title Pd-catalyzed intramolecular addition of active methylene compounds to alkynes with subsequent cross-coupling with (hetero)aryl halides
title_full Pd-catalyzed intramolecular addition of active methylene compounds to alkynes with subsequent cross-coupling with (hetero)aryl halides
title_fullStr Pd-catalyzed intramolecular addition of active methylene compounds to alkynes with subsequent cross-coupling with (hetero)aryl halides
title_full_unstemmed Pd-catalyzed intramolecular addition of active methylene compounds to alkynes with subsequent cross-coupling with (hetero)aryl halides
title_short Pd-catalyzed intramolecular addition of active methylene compounds to alkynes with subsequent cross-coupling with (hetero)aryl halides
title_sort pd-catalyzed intramolecular addition of active methylene compounds to alkynes with subsequent cross-coupling with (hetero)aryl halides
topic Chemistry
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9076196/
https://www.ncbi.nlm.nih.gov/pubmed/35541417
http://dx.doi.org/10.1039/c9ra08002c
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