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Tris(pentafluorophenyl)borane‐Catalyzed Carbenium Ion Generation and Autocatalytic Pyrazole Synthesis—A Computational and Experimental Study

In recent years, metal‐free organic synthesis using triarylboranes as catalysts has become a prevalent research area. Herein we report a comprehensive computational and experimental study for the highly selective synthesis of N‐substituted pyrazoles through the generation of carbenium species from t...

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Autores principales: Dasgupta, Ayan, Babaahmadi, Rasool, Pahar, Sanjukta, Stefkova, Katarina, Gierlichs, Lukas, Yates, Brian F., Ariafard, Alireza, Melen, Rebecca L.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: John Wiley and Sons Inc. 2021
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8596400/
https://www.ncbi.nlm.nih.gov/pubmed/34590773
http://dx.doi.org/10.1002/anie.202109744
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author Dasgupta, Ayan
Babaahmadi, Rasool
Pahar, Sanjukta
Stefkova, Katarina
Gierlichs, Lukas
Yates, Brian F.
Ariafard, Alireza
Melen, Rebecca L.
author_facet Dasgupta, Ayan
Babaahmadi, Rasool
Pahar, Sanjukta
Stefkova, Katarina
Gierlichs, Lukas
Yates, Brian F.
Ariafard, Alireza
Melen, Rebecca L.
author_sort Dasgupta, Ayan
collection PubMed
description In recent years, metal‐free organic synthesis using triarylboranes as catalysts has become a prevalent research area. Herein we report a comprehensive computational and experimental study for the highly selective synthesis of N‐substituted pyrazoles through the generation of carbenium species from the reaction between aryl esters and vinyl diazoacetates in the presence of catalytic tris(pentafluorophenyl)borane [B(C(6)F(5))(3)]. DFT studies were undertaken to illuminate the reaction mechanism revealing that the in situ generation of a carbenium species acts as an autocatalyst to prompt the regiospecific formation of N‐substituted pyrazoles in good to excellent yields (up to 81 %).
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spelling pubmed-85964002021-11-22 Tris(pentafluorophenyl)borane‐Catalyzed Carbenium Ion Generation and Autocatalytic Pyrazole Synthesis—A Computational and Experimental Study Dasgupta, Ayan Babaahmadi, Rasool Pahar, Sanjukta Stefkova, Katarina Gierlichs, Lukas Yates, Brian F. Ariafard, Alireza Melen, Rebecca L. Angew Chem Int Ed Engl Communications In recent years, metal‐free organic synthesis using triarylboranes as catalysts has become a prevalent research area. Herein we report a comprehensive computational and experimental study for the highly selective synthesis of N‐substituted pyrazoles through the generation of carbenium species from the reaction between aryl esters and vinyl diazoacetates in the presence of catalytic tris(pentafluorophenyl)borane [B(C(6)F(5))(3)]. DFT studies were undertaken to illuminate the reaction mechanism revealing that the in situ generation of a carbenium species acts as an autocatalyst to prompt the regiospecific formation of N‐substituted pyrazoles in good to excellent yields (up to 81 %). John Wiley and Sons Inc. 2021-10-12 2021-11-08 /pmc/articles/PMC8596400/ /pubmed/34590773 http://dx.doi.org/10.1002/anie.202109744 Text en © 2021 The Authors. Angewandte Chemie International Edition 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 Communications
Dasgupta, Ayan
Babaahmadi, Rasool
Pahar, Sanjukta
Stefkova, Katarina
Gierlichs, Lukas
Yates, Brian F.
Ariafard, Alireza
Melen, Rebecca L.
Tris(pentafluorophenyl)borane‐Catalyzed Carbenium Ion Generation and Autocatalytic Pyrazole Synthesis—A Computational and Experimental Study
title Tris(pentafluorophenyl)borane‐Catalyzed Carbenium Ion Generation and Autocatalytic Pyrazole Synthesis—A Computational and Experimental Study
title_full Tris(pentafluorophenyl)borane‐Catalyzed Carbenium Ion Generation and Autocatalytic Pyrazole Synthesis—A Computational and Experimental Study
title_fullStr Tris(pentafluorophenyl)borane‐Catalyzed Carbenium Ion Generation and Autocatalytic Pyrazole Synthesis—A Computational and Experimental Study
title_full_unstemmed Tris(pentafluorophenyl)borane‐Catalyzed Carbenium Ion Generation and Autocatalytic Pyrazole Synthesis—A Computational and Experimental Study
title_short Tris(pentafluorophenyl)borane‐Catalyzed Carbenium Ion Generation and Autocatalytic Pyrazole Synthesis—A Computational and Experimental Study
title_sort tris(pentafluorophenyl)borane‐catalyzed carbenium ion generation and autocatalytic pyrazole synthesis—a computational and experimental study
topic Communications
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8596400/
https://www.ncbi.nlm.nih.gov/pubmed/34590773
http://dx.doi.org/10.1002/anie.202109744
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