Photo-Organocatalytic Enantioselective Radical Cascade Enabled by Single-Electron Transfer Activation of Allenes

Allenes are commonly used in metal-mediated transformations, cycloaddition reactions, and radical processes. However, their activation by single-electron transfer (SET) is largely underexplored. Herein, we report a visible light-driven enantioselective organocatalytic process that uses the excited-s...

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Autores: Perego, Luca Alessandro, Bonilla, Pablo, Melchiorre, Paolo
Tipo de recurso: artículo
Estado:Versión aceptada para publicación
Fecha de publicación:2019
País:España
Institución:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
Repositorio:Recercat. Dipósit de la Recerca de Catalunya
OAI Identifier:oai:recercat.cat:2072/376312
Acceso en línea:http://hdl.handle.net/2072/376312
https://doi.org/10.1002/adsc.201900973
Access Level:acceso abierto
Palabra clave:54
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spelling Photo-Organocatalytic Enantioselective Radical Cascade Enabled by Single-Electron Transfer Activation of AllenesPerego, Luca AlessandroBonilla, PabloMelchiorre, Paolo54Allenes are commonly used in metal-mediated transformations, cycloaddition reactions, and radical processes. However, their activation by single-electron transfer (SET) is largely underexplored. Herein, we report a visible light-driven enantioselective organocatalytic process that uses the excited-state reactivity of chiral iminium ions to activate allenes by SET oxidation. The ensuing allene cation radicals participate in stereocontrolled cascade reactions to deliver chiral bicyclic scaffolds with good enantioselectivity and exquisite diastereoselectivity. Density Functional Theory (DFT) calculations support a mechanism that combines the peculiar chemistry of allene radical cations with polar reactivity.2019info:eu-repo/semantics/articleinfo:eu-repo/semantics/acceptedVersion302 p.application/pdfhttp://hdl.handle.net/2072/376312https://doi.org/10.1002/adsc.201900973RECERCAT (Dipòsit de la Recerca de Catalunya)reponame:Recercat. Dipósit de la Recerca de Catalunyainstname:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)InglésMICIU (CTQ2016-75520-P)AGAUR (Grant 2017 SGR 981)ERC-2015-CoG 681840 - CATA-LUXL'accés als continguts d'aquest document queda condicionat a l'acceptació de les condicions d'ús establertes per la següent llicència Creative Commons:http://creativecommons.org/licenses/by-nc-nd/4.0/info:eu-repo/semantics/openAccessoai:recercat.cat:2072/3763122026-05-29T05:05:01Z
dc.title.none.fl_str_mv Photo-Organocatalytic Enantioselective Radical Cascade Enabled by Single-Electron Transfer Activation of Allenes
title Photo-Organocatalytic Enantioselective Radical Cascade Enabled by Single-Electron Transfer Activation of Allenes
spellingShingle Photo-Organocatalytic Enantioselective Radical Cascade Enabled by Single-Electron Transfer Activation of Allenes
Perego, Luca Alessandro
54
title_short Photo-Organocatalytic Enantioselective Radical Cascade Enabled by Single-Electron Transfer Activation of Allenes
title_full Photo-Organocatalytic Enantioselective Radical Cascade Enabled by Single-Electron Transfer Activation of Allenes
title_fullStr Photo-Organocatalytic Enantioselective Radical Cascade Enabled by Single-Electron Transfer Activation of Allenes
title_full_unstemmed Photo-Organocatalytic Enantioselective Radical Cascade Enabled by Single-Electron Transfer Activation of Allenes
title_sort Photo-Organocatalytic Enantioselective Radical Cascade Enabled by Single-Electron Transfer Activation of Allenes
dc.creator.none.fl_str_mv Perego, Luca Alessandro
Bonilla, Pablo
Melchiorre, Paolo
author Perego, Luca Alessandro
author_facet Perego, Luca Alessandro
Bonilla, Pablo
Melchiorre, Paolo
author_role author
author2 Bonilla, Pablo
Melchiorre, Paolo
author2_role author
author
dc.subject.none.fl_str_mv 54
topic 54
description Allenes are commonly used in metal-mediated transformations, cycloaddition reactions, and radical processes. However, their activation by single-electron transfer (SET) is largely underexplored. Herein, we report a visible light-driven enantioselective organocatalytic process that uses the excited-state reactivity of chiral iminium ions to activate allenes by SET oxidation. The ensuing allene cation radicals participate in stereocontrolled cascade reactions to deliver chiral bicyclic scaffolds with good enantioselectivity and exquisite diastereoselectivity. Density Functional Theory (DFT) calculations support a mechanism that combines the peculiar chemistry of allene radical cations with polar reactivity.
publishDate 2019
dc.date.none.fl_str_mv 2019
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/acceptedVersion
format article
status_str acceptedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/2072/376312
https://doi.org/10.1002/adsc.201900973
url http://hdl.handle.net/2072/376312
https://doi.org/10.1002/adsc.201900973
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv MICIU (CTQ2016-75520-P)
AGAUR (Grant 2017 SGR 981)
ERC-2015-CoG 681840 - CATA-LUX
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv 302 p.
application/pdf
dc.source.none.fl_str_mv RECERCAT (Dipòsit de la Recerca de Catalunya)
reponame:Recercat. Dipósit de la Recerca de Catalunya
instname:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
instname_str Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
reponame_str Recercat. Dipósit de la Recerca de Catalunya
collection Recercat. Dipósit de la Recerca de Catalunya
repository.name.fl_str_mv
repository.mail.fl_str_mv
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score 15,811543

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