Catalytic Asymmetric α-Functionalization of α-Branched Aldehydes

Aldehydes constitute a main class of organic compounds widely applied in synthesis. As such, catalyst-controlled enantioselective α-functionalization of aldehydes has attracted great interest over the years. In this context, α-branched aldehydes are especially challenging substrates because of react...

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Autores: Vera Salas, Silvia, Landa Álvarez, Aitor, Mielgo Vicente, María Antonia, Gamboa Landa, José Ignacio, Oyarbide Garmendia, Juan Miguel, Soloshonok, Vadym Anatolievch
Tipo de recurso: artículo
Fecha de publicación:2023
País:España
Institución:Universidad del País Vasco
Repositorio:Addi. Archivo Digital para la Docencia y la Investigación
OAI Identifier:oai:addi.ehu.eus:10810/60550
Acceso en línea:http://hdl.handle.net/10810/60550
Access Level:acceso abierto
Palabra clave:aldehydes
asymmetric catalysis
quaternary carbon
organocatalysis
dual catalysis
reaction umpolung
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spelling Catalytic Asymmetric α-Functionalization of α-Branched AldehydesVera Salas, SilviaLanda Álvarez, AitorMielgo Vicente, María AntoniaGamboa Landa, José IgnacioOyarbide Garmendia, Juan MiguelSoloshonok, Vadym Anatolievchaldehydesasymmetric catalysisquaternary carbonorganocatalysisdual catalysisreaction umpolungAldehydes constitute a main class of organic compounds widely applied in synthesis. As such, catalyst-controlled enantioselective α-functionalization of aldehydes has attracted great interest over the years. In this context, α-branched aldehydes are especially challenging substrates because of reactivity and selectivity issues. Firstly, the transient trisubstituted enamines and enolates resulting upon treatment with an aminocatalyst or a base, respectively, would exhibit attenuated reactivity; secondly, mixtures of E- and Z-configured enamines/enolates may be formed; and third, effective face-discrimination on such trisubstituted sp2 carbon intermediates by the incoming electrophilic reagent is not trivial. Despite these issues, in the last 15 years, several catalytic approaches for the α-functionalization of prostereogenic α-branched aldehydes that proceed in useful yields and diastereo- and enantioselectivity have been uncovered. Developments include both organocatalytic and metal-catalyzed approaches as well as dual catalysis strategies for forging new carbon–carbon and carbon–heteroatom (C-O, N, S, F, Cl, Br, …) bond formation at Cα of the starting aldehyde. In this review, some key early contributions to the field are presented, but focus is on the most recent methods, mainly covering the literature from year 2014 onward.This research was funded by Basque Government (grant IT-1583-22) and by MCIN/AEI/10.13039/501100011033 (grant PID2019-109633GB-C21).MDPI2023202320232023info:eu-repo/semantics/articleapplication/pdfhttp://hdl.handle.net/10810/60550reponame:Addi. Archivo Digital para la Docencia y la Investigacióninstname:Universidad del País VascoInglésinfo:eu-repo/grantAgreement/MICINN/PID2019-109633GB-C21/https://www.mdpi.com/1420-3049/28/6/2694info:eu-repo/semantics/openAccesshttp://creativecommons.org/licenses/by/4.0/© 2023 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (https://creativecommons.org/licenses/by/ 4.0/).oai:addi.ehu.eus:10810/605502026-06-18T09:23:17Z
dc.title.none.fl_str_mv Catalytic Asymmetric α-Functionalization of α-Branched Aldehydes
title Catalytic Asymmetric α-Functionalization of α-Branched Aldehydes
spellingShingle Catalytic Asymmetric α-Functionalization of α-Branched Aldehydes
Vera Salas, Silvia
aldehydes
asymmetric catalysis
quaternary carbon
organocatalysis
dual catalysis
reaction umpolung
title_short Catalytic Asymmetric α-Functionalization of α-Branched Aldehydes
title_full Catalytic Asymmetric α-Functionalization of α-Branched Aldehydes
title_fullStr Catalytic Asymmetric α-Functionalization of α-Branched Aldehydes
title_full_unstemmed Catalytic Asymmetric α-Functionalization of α-Branched Aldehydes
title_sort Catalytic Asymmetric α-Functionalization of α-Branched Aldehydes
dc.creator.none.fl_str_mv Vera Salas, Silvia
Landa Álvarez, Aitor
Mielgo Vicente, María Antonia
Gamboa Landa, José Ignacio
Oyarbide Garmendia, Juan Miguel
Soloshonok, Vadym Anatolievch
author Vera Salas, Silvia
author_facet Vera Salas, Silvia
Landa Álvarez, Aitor
Mielgo Vicente, María Antonia
Gamboa Landa, José Ignacio
Oyarbide Garmendia, Juan Miguel
Soloshonok, Vadym Anatolievch
author_role author
author2 Landa Álvarez, Aitor
Mielgo Vicente, María Antonia
Gamboa Landa, José Ignacio
Oyarbide Garmendia, Juan Miguel
Soloshonok, Vadym Anatolievch
author2_role author
author
author
author
author
dc.subject.none.fl_str_mv aldehydes
asymmetric catalysis
quaternary carbon
organocatalysis
dual catalysis
reaction umpolung
topic aldehydes
asymmetric catalysis
quaternary carbon
organocatalysis
dual catalysis
reaction umpolung
description Aldehydes constitute a main class of organic compounds widely applied in synthesis. As such, catalyst-controlled enantioselective α-functionalization of aldehydes has attracted great interest over the years. In this context, α-branched aldehydes are especially challenging substrates because of reactivity and selectivity issues. Firstly, the transient trisubstituted enamines and enolates resulting upon treatment with an aminocatalyst or a base, respectively, would exhibit attenuated reactivity; secondly, mixtures of E- and Z-configured enamines/enolates may be formed; and third, effective face-discrimination on such trisubstituted sp2 carbon intermediates by the incoming electrophilic reagent is not trivial. Despite these issues, in the last 15 years, several catalytic approaches for the α-functionalization of prostereogenic α-branched aldehydes that proceed in useful yields and diastereo- and enantioselectivity have been uncovered. Developments include both organocatalytic and metal-catalyzed approaches as well as dual catalysis strategies for forging new carbon–carbon and carbon–heteroatom (C-O, N, S, F, Cl, Br, …) bond formation at Cα of the starting aldehyde. In this review, some key early contributions to the field are presented, but focus is on the most recent methods, mainly covering the literature from year 2014 onward.
publishDate 2023
dc.date.none.fl_str_mv 2023
2023
2023
2023
dc.type.none.fl_str_mv info:eu-repo/semantics/article
format article
dc.identifier.none.fl_str_mv http://hdl.handle.net/10810/60550
url http://hdl.handle.net/10810/60550
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv info:eu-repo/grantAgreement/MICINN/PID2019-109633GB-C21/
https://www.mdpi.com/1420-3049/28/6/2694
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
http://creativecommons.org/licenses/by/4.0/
eu_rights_str_mv openAccess
rights_invalid_str_mv http://creativecommons.org/licenses/by/4.0/
dc.format.none.fl_str_mv application/pdf
dc.publisher.none.fl_str_mv MDPI
publisher.none.fl_str_mv MDPI
dc.source.none.fl_str_mv reponame:Addi. Archivo Digital para la Docencia y la Investigación
instname:Universidad del País Vasco
instname_str Universidad del País Vasco
reponame_str Addi. Archivo Digital para la Docencia y la Investigación
collection Addi. Archivo Digital para la Docencia y la Investigación
repository.name.fl_str_mv
repository.mail.fl_str_mv
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