Mechanistically Guided Design of an Efficient and Enantioselective Aminocatalytic α-Chlorination of Aldehydes

[Image: see text] The enantioselective aminocatalytic α-chlorination of aldehydes is a challenging reaction because of its tendency to proceed through neutral intermediates in unselective pathways. Herein we report the rational shift to a highly selective reaction pathway involving charged intermedi...

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Autores principales: Hutchinson, George, Alamillo-Ferrer, Carla, Burés, Jordi
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2021
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8297727/
https://www.ncbi.nlm.nih.gov/pubmed/33929823
http://dx.doi.org/10.1021/jacs.1c02997
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author Hutchinson, George
Alamillo-Ferrer, Carla
Burés, Jordi
author_facet Hutchinson, George
Alamillo-Ferrer, Carla
Burés, Jordi
author_sort Hutchinson, George
collection PubMed
description [Image: see text] The enantioselective aminocatalytic α-chlorination of aldehydes is a challenging reaction because of its tendency to proceed through neutral intermediates in unselective pathways. Herein we report the rational shift to a highly selective reaction pathway involving charged intermediates using hexafluoroisopropanol as solvent. This change in mechanism has enabled us to match and improve upon the yields and enantioselectivities displayed by previous methods while using cheaper aminocatalysts and chlorinating agents, 80–95% less amount of catalyst, convenient temperatures, and shorter reaction times.
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spelling pubmed-82977272021-07-23 Mechanistically Guided Design of an Efficient and Enantioselective Aminocatalytic α-Chlorination of Aldehydes Hutchinson, George Alamillo-Ferrer, Carla Burés, Jordi J Am Chem Soc [Image: see text] The enantioselective aminocatalytic α-chlorination of aldehydes is a challenging reaction because of its tendency to proceed through neutral intermediates in unselective pathways. Herein we report the rational shift to a highly selective reaction pathway involving charged intermediates using hexafluoroisopropanol as solvent. This change in mechanism has enabled us to match and improve upon the yields and enantioselectivities displayed by previous methods while using cheaper aminocatalysts and chlorinating agents, 80–95% less amount of catalyst, convenient temperatures, and shorter reaction times. American Chemical Society 2021-04-30 2021-05-12 /pmc/articles/PMC8297727/ /pubmed/33929823 http://dx.doi.org/10.1021/jacs.1c02997 Text en © 2021 American Chemical Society Permits the broadest form of re-use including for commercial purposes, provided that author attribution and integrity are maintained (https://creativecommons.org/licenses/by/4.0/).
spellingShingle Hutchinson, George
Alamillo-Ferrer, Carla
Burés, Jordi
Mechanistically Guided Design of an Efficient and Enantioselective Aminocatalytic α-Chlorination of Aldehydes
title Mechanistically Guided Design of an Efficient and Enantioselective Aminocatalytic α-Chlorination of Aldehydes
title_full Mechanistically Guided Design of an Efficient and Enantioselective Aminocatalytic α-Chlorination of Aldehydes
title_fullStr Mechanistically Guided Design of an Efficient and Enantioselective Aminocatalytic α-Chlorination of Aldehydes
title_full_unstemmed Mechanistically Guided Design of an Efficient and Enantioselective Aminocatalytic α-Chlorination of Aldehydes
title_short Mechanistically Guided Design of an Efficient and Enantioselective Aminocatalytic α-Chlorination of Aldehydes
title_sort mechanistically guided design of an efficient and enantioselective aminocatalytic α-chlorination of aldehydes
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8297727/
https://www.ncbi.nlm.nih.gov/pubmed/33929823
http://dx.doi.org/10.1021/jacs.1c02997
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AT alamilloferrercarla mechanisticallyguideddesignofanefficientandenantioselectiveaminocatalyticachlorinationofaldehydes
AT buresjordi mechanisticallyguideddesignofanefficientandenantioselectiveaminocatalyticachlorinationofaldehydes

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