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Photo‐Organocatalytic Enantioselective Radical Cascade Reactions of Unactivated Olefins

Radical cascade processes are invaluable for their ability to rapidly construct complex chiral molecules from simple substrates. However, implementing catalytic asymmetric variants is difficult. Reported herein is a visible‐light‐mediated organocatalytic strategy that exploits the excited‐state reac...

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Autores principales: Bonilla, Pablo, Rey, Yannick P., Holden, Catherine M., Melchiorre, Paolo
Formato: Online Artículo Texto
Lenguaje:English
Publicado: John Wiley and Sons Inc. 2018
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6175195/
https://www.ncbi.nlm.nih.gov/pubmed/30098097
http://dx.doi.org/10.1002/anie.201808183
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author Bonilla, Pablo
Rey, Yannick P.
Holden, Catherine M.
Melchiorre, Paolo
author_facet Bonilla, Pablo
Rey, Yannick P.
Holden, Catherine M.
Melchiorre, Paolo
author_sort Bonilla, Pablo
collection PubMed
description Radical cascade processes are invaluable for their ability to rapidly construct complex chiral molecules from simple substrates. However, implementing catalytic asymmetric variants is difficult. Reported herein is a visible‐light‐mediated organocatalytic strategy that exploits the excited‐state reactivity of chiral iminium ions to trigger radical cascade reactions with high enantioselectivity. By combining two sequential radical‐based bond‐forming events, the method converts unactivated olefins and α,β‐unsaturated aldehydes into chiral adducts in a single step. The implementation of an asymmetric three‐component radical cascade further demonstrates the complexity‐generating power of this photochemical strategy.
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spelling pubmed-61751952018-10-15 Photo‐Organocatalytic Enantioselective Radical Cascade Reactions of Unactivated Olefins Bonilla, Pablo Rey, Yannick P. Holden, Catherine M. Melchiorre, Paolo Angew Chem Int Ed Engl Communications Radical cascade processes are invaluable for their ability to rapidly construct complex chiral molecules from simple substrates. However, implementing catalytic asymmetric variants is difficult. Reported herein is a visible‐light‐mediated organocatalytic strategy that exploits the excited‐state reactivity of chiral iminium ions to trigger radical cascade reactions with high enantioselectivity. By combining two sequential radical‐based bond‐forming events, the method converts unactivated olefins and α,β‐unsaturated aldehydes into chiral adducts in a single step. The implementation of an asymmetric three‐component radical cascade further demonstrates the complexity‐generating power of this photochemical strategy. John Wiley and Sons Inc. 2018-08-31 2018-09-24 /pmc/articles/PMC6175195/ /pubmed/30098097 http://dx.doi.org/10.1002/anie.201808183 Text en © 2018 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the http://creativecommons.org/licenses/by-nc-nd/4.0/ License, which permits use and distribution in any medium, provided the original work is properly cited, the use is non‐commercial and no modifications or adaptations are made.
spellingShingle Communications
Bonilla, Pablo
Rey, Yannick P.
Holden, Catherine M.
Melchiorre, Paolo
Photo‐Organocatalytic Enantioselective Radical Cascade Reactions of Unactivated Olefins
title Photo‐Organocatalytic Enantioselective Radical Cascade Reactions of Unactivated Olefins
title_full Photo‐Organocatalytic Enantioselective Radical Cascade Reactions of Unactivated Olefins
title_fullStr Photo‐Organocatalytic Enantioselective Radical Cascade Reactions of Unactivated Olefins
title_full_unstemmed Photo‐Organocatalytic Enantioselective Radical Cascade Reactions of Unactivated Olefins
title_short Photo‐Organocatalytic Enantioselective Radical Cascade Reactions of Unactivated Olefins
title_sort photo‐organocatalytic enantioselective radical cascade reactions of unactivated olefins
topic Communications
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6175195/
https://www.ncbi.nlm.nih.gov/pubmed/30098097
http://dx.doi.org/10.1002/anie.201808183
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