Stereoselective cis-Vinylcyclopropanation via a Gold(I)-Catalyzed Retro-Buchner Reaction under Mild Conditions

A highly stereoselective gold(I)-catalyzed cis- vinylcyclopropanation of alkenes has been developed. Allylic gold carbenes, generated via a retro-Buchner reaction of 7- alkenyl-1,3,5-cycloheptatrienes, react with alkenes to form vinylcyclopropanes. The gold(I)-catalyzed retro-Buchner reac- tion of t...

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Detalles Bibliográficos
Autores: Herle, Bart, Holstein, Philipp M., Echavarren, Antonio M.
Tipo de recurso: artículo
Estado:Versión aceptada para publicación
Fecha de publicación:2017
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:2072/335514
Acceso en línea:http://hdl.handle.net/2072/335514
https://doi.org/10.1021/acscatal.7b00737
Access Level:acceso abierto
Palabra clave:54
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spelling Stereoselective cis-Vinylcyclopropanation via a Gold(I)-Catalyzed Retro-Buchner Reaction under Mild ConditionsHerle, BartHolstein, Philipp M.Echavarren, Antonio M.54A highly stereoselective gold(I)-catalyzed cis- vinylcyclopropanation of alkenes has been developed. Allylic gold carbenes, generated via a retro-Buchner reaction of 7- alkenyl-1,3,5-cycloheptatrienes, react with alkenes to form vinylcyclopropanes. The gold(I)-catalyzed retro-Buchner reac- tion of these substrates proceeds by simple heating at a temperature much lower than that required for the reaction of 7- aryl-1,3,5-cycloheptatrienes (75 °C vs 120 °C). A newly developed Julia−Kocienski reagent enables the synthesis of the required cycloheptatriene derivatives in one step from readily available aldehydes or ketones. On the basis of mechanistic investigations, a stereochemical model for the cis selectivity was proposed. An unprecedented gold-catalyzed isomerization of cis- to trans-cyclopropanes has also been discovered and studied by DFT calculations.2017info:eu-repo/semantics/articleinfo:eu-repo/semantics/acceptedVersion3668 p.application/pdfhttp://hdl.handle.net/2072/335514https://doi.org/10.1021/acscatal.7b00737RECERCAT (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)Inglésinfo:eu-repo/grantAgreement/EC/FP7/321066L'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:2072/3355142026-05-29T05:05:01Z
dc.title.none.fl_str_mv Stereoselective cis-Vinylcyclopropanation via a Gold(I)-Catalyzed Retro-Buchner Reaction under Mild Conditions
title Stereoselective cis-Vinylcyclopropanation via a Gold(I)-Catalyzed Retro-Buchner Reaction under Mild Conditions
spellingShingle Stereoselective cis-Vinylcyclopropanation via a Gold(I)-Catalyzed Retro-Buchner Reaction under Mild Conditions
Herle, Bart
54
title_short Stereoselective cis-Vinylcyclopropanation via a Gold(I)-Catalyzed Retro-Buchner Reaction under Mild Conditions
title_full Stereoselective cis-Vinylcyclopropanation via a Gold(I)-Catalyzed Retro-Buchner Reaction under Mild Conditions
title_fullStr Stereoselective cis-Vinylcyclopropanation via a Gold(I)-Catalyzed Retro-Buchner Reaction under Mild Conditions
title_full_unstemmed Stereoselective cis-Vinylcyclopropanation via a Gold(I)-Catalyzed Retro-Buchner Reaction under Mild Conditions
title_sort Stereoselective cis-Vinylcyclopropanation via a Gold(I)-Catalyzed Retro-Buchner Reaction under Mild Conditions
dc.creator.none.fl_str_mv Herle, Bart
Holstein, Philipp M.
Echavarren, Antonio M.
author Herle, Bart
author_facet Herle, Bart
Holstein, Philipp M.
Echavarren, Antonio M.
author_role author
author2 Holstein, Philipp M.
Echavarren, Antonio M.
author2_role author
author
dc.subject.none.fl_str_mv 54
topic 54
description A highly stereoselective gold(I)-catalyzed cis- vinylcyclopropanation of alkenes has been developed. Allylic gold carbenes, generated via a retro-Buchner reaction of 7- alkenyl-1,3,5-cycloheptatrienes, react with alkenes to form vinylcyclopropanes. The gold(I)-catalyzed retro-Buchner reac- tion of these substrates proceeds by simple heating at a temperature much lower than that required for the reaction of 7- aryl-1,3,5-cycloheptatrienes (75 °C vs 120 °C). A newly developed Julia−Kocienski reagent enables the synthesis of the required cycloheptatriene derivatives in one step from readily available aldehydes or ketones. On the basis of mechanistic investigations, a stereochemical model for the cis selectivity was proposed. An unprecedented gold-catalyzed isomerization of cis- to trans-cyclopropanes has also been discovered and studied by DFT calculations.
publishDate 2017
dc.date.none.fl_str_mv 2017
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/2072/335514
https://doi.org/10.1021/acscatal.7b00737
url http://hdl.handle.net/2072/335514
https://doi.org/10.1021/acscatal.7b00737
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv info:eu-repo/grantAgreement/EC/FP7/321066
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv 3668 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
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