Direct Synthesis of α‐Aryl‐α‐Trifluoromethyl Alcohols via Nickel Catalyzed Cross‐Electrophile Coupling

A nickel‐catalyzed reductive cross‐electrophile coupling between the redox‐active N‐trifluoroethoxyphthalimide and iodoarenes is documented. The protocol reproduces a formal arylation of trifluoroacetaldehyde under mild conditions in high yields (up to 88 %) and with large functional group tolerance...

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Autores principales: Lombardi, Lorenzo, Cerveri, Alessandro, Giovanelli, Riccardo, Castiñeira Reis, Marta, Silva López, Carlos, Bertuzzi, Giulio, Bandini, Marco
Formato: Online Artículo Texto
Lenguaje:English
Publicado: John Wiley and Sons Inc. 2022
Materias:
Communications
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9828748/
https://www.ncbi.nlm.nih.gov/pubmed/36161744
http://dx.doi.org/10.1002/anie.202211732
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author Lombardi, Lorenzo
Cerveri, Alessandro
Giovanelli, Riccardo
Castiñeira Reis, Marta
Silva López, Carlos
Bertuzzi, Giulio
Bandini, Marco
author_facet Lombardi, Lorenzo
Cerveri, Alessandro
Giovanelli, Riccardo
Castiñeira Reis, Marta
Silva López, Carlos
Bertuzzi, Giulio
Bandini, Marco
author_sort Lombardi, Lorenzo
collection PubMed
description A nickel‐catalyzed reductive cross‐electrophile coupling between the redox‐active N‐trifluoroethoxyphthalimide and iodoarenes is documented. The protocol reproduces a formal arylation of trifluoroacetaldehyde under mild conditions in high yields (up to 88 %) and with large functional group tolerance (30 examples). A combined computational and experimental investigation revealed a pivotal solvent assisted 1,2‐Hydrogen Atom Transfer (HAT) process to generate a nucleophilic α‐hydroxy‐α‐trifluoromethyl C‐centered radical for the Csp(2)−Csp(3) bond forming process.
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spelling pubmed-98287482023-01-10 Direct Synthesis of α‐Aryl‐α‐Trifluoromethyl Alcohols via Nickel Catalyzed Cross‐Electrophile Coupling Lombardi, Lorenzo Cerveri, Alessandro Giovanelli, Riccardo Castiñeira Reis, Marta Silva López, Carlos Bertuzzi, Giulio Bandini, Marco Angew Chem Int Ed Engl Communications A nickel‐catalyzed reductive cross‐electrophile coupling between the redox‐active N‐trifluoroethoxyphthalimide and iodoarenes is documented. The protocol reproduces a formal arylation of trifluoroacetaldehyde under mild conditions in high yields (up to 88 %) and with large functional group tolerance (30 examples). A combined computational and experimental investigation revealed a pivotal solvent assisted 1,2‐Hydrogen Atom Transfer (HAT) process to generate a nucleophilic α‐hydroxy‐α‐trifluoromethyl C‐centered radical for the Csp(2)−Csp(3) bond forming process. John Wiley and Sons Inc. 2022-10-18 2022-11-21 /pmc/articles/PMC9828748/ /pubmed/36161744 http://dx.doi.org/10.1002/anie.202211732 Text en © 2022 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
Lombardi, Lorenzo
Cerveri, Alessandro
Giovanelli, Riccardo
Castiñeira Reis, Marta
Silva López, Carlos
Bertuzzi, Giulio
Bandini, Marco
Direct Synthesis of α‐Aryl‐α‐Trifluoromethyl Alcohols via Nickel Catalyzed Cross‐Electrophile Coupling
title Direct Synthesis of α‐Aryl‐α‐Trifluoromethyl Alcohols via Nickel Catalyzed Cross‐Electrophile Coupling
title_full Direct Synthesis of α‐Aryl‐α‐Trifluoromethyl Alcohols via Nickel Catalyzed Cross‐Electrophile Coupling
title_fullStr Direct Synthesis of α‐Aryl‐α‐Trifluoromethyl Alcohols via Nickel Catalyzed Cross‐Electrophile Coupling
title_full_unstemmed Direct Synthesis of α‐Aryl‐α‐Trifluoromethyl Alcohols via Nickel Catalyzed Cross‐Electrophile Coupling
title_short Direct Synthesis of α‐Aryl‐α‐Trifluoromethyl Alcohols via Nickel Catalyzed Cross‐Electrophile Coupling
title_sort direct synthesis of α‐aryl‐α‐trifluoromethyl alcohols via nickel catalyzed cross‐electrophile coupling
topic Communications
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9828748/
https://www.ncbi.nlm.nih.gov/pubmed/36161744
http://dx.doi.org/10.1002/anie.202211732
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