Catalytic regioselective isomerization of 2,2-disubstituted oxetanes to homoallylic alcohols

The selective isomerization of strained heterocyclic compounds is an important tool in organic synthesis. An unprecedented regioselective isomerization of 2,2-disubstituted oxetanes into homoallylic alcohols is described. The use of tris(pentafluorophenyl)borane (B(C6F5)3), a commercially available...

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Autores: Cabré, Albert|||0000-0003-4367-2635, Rafael, Sergi, Sciortino, Giuseppe|||0000-0001-9657-1788, Ujaque, Gregori|||0000-0001-5896-9998, Verdaguer, Xavier|||0000-0002-9229-969X, Lledós, Agustí|||0000-0001-7909-422X, Riera, Antoni|||0000-0001-7142-7675
Tipo de recurso: artículo
Fecha de publicación:2020
País:España
Institución:Universitat Autònoma de Barcelona
Repositorio:Dipòsit Digital de Documents de la UAB
Idioma:inglés
OAI Identifier:oai:ddd.uab.cat:279264
Acceso en línea:https://ddd.uab.cat/record/279264
https://dx.doi.org/urn:doi:10.1002/anie.201915772
Access Level:acceso abierto
Palabra clave:Allylic compounds
Asymmetric catalysis
Boron
Hydrogenation
Isomerization
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spelling Catalytic regioselective isomerization of 2,2-disubstituted oxetanes to homoallylic alcoholsCabré, Albert|||0000-0003-4367-2635Rafael, SergiSciortino, Giuseppe|||0000-0001-9657-1788Ujaque, Gregori|||0000-0001-5896-9998Verdaguer, Xavier|||0000-0002-9229-969XLledós, Agustí|||0000-0001-7909-422XRiera, Antoni|||0000-0001-7142-7675Allylic compoundsAsymmetric catalysisBoronHydrogenationIsomerizationThe selective isomerization of strained heterocyclic compounds is an important tool in organic synthesis. An unprecedented regioselective isomerization of 2,2-disubstituted oxetanes into homoallylic alcohols is described. The use of tris(pentafluorophenyl)borane (B(C6F5)3), a commercially available Lewis acid was key to obtaining good yields and selectivities since other Lewis acids afforded mixtures of isomers and substantial polymerization. The reaction took place under exceptionally mild reaction conditions and very low catalyst loading (0.5 mol %). DFT calculations disclose the mechanistic features of the isomerization and account for the high selectivity displayed by the B(C6F5)3 catalyst. The synthetic applicability of the new reaction is demonstrated by the preparation of γ-chiral alcohols using iridium-catalyzed asymmetric hydrogenation. 22020-01-0120202020-01-01Articlehttp://purl.org/coar/resource_type/c_6501AMhttp://purl.org/coar/version/c_ab4af688f83e57aainfo:eu-repo/semantics/articleapplication/pdfhttps://ddd.uab.cat/record/279264https://dx.doi.org/urn:doi:10.1002/anie.201915772reponame:Dipòsit Digital de Documents de la UABinstname:Universitat Autònoma de BarcelonaInglésengAgencia Estatal de Investigación https://doi.org/10.13039/501100011033 CTQ2017-87840-PAgencia Estatal de Investigación https://doi.org/10.13039/501100011033 CTQ2017-87889-Popen accesshttp://purl.org/coar/access_right/c_abf2Aquest material està protegit per drets d'autor i/o drets afins. Podeu utilitzar aquest material en funció del que permet la legislació de drets d'autor i drets afins d'aplicació al vostre cas. Per a d'altres usos heu d'obtenir permís del(s) titular(s) de drets.https://rightsstatements.org/vocab/InC/1.0/info:eu-repo/semantics/openAccessoai:ddd.uab.cat:2792642026-06-06T12:50:31Z
dc.title.none.fl_str_mv Catalytic regioselective isomerization of 2,2-disubstituted oxetanes to homoallylic alcohols
title Catalytic regioselective isomerization of 2,2-disubstituted oxetanes to homoallylic alcohols
spellingShingle Catalytic regioselective isomerization of 2,2-disubstituted oxetanes to homoallylic alcohols
Cabré, Albert|||0000-0003-4367-2635
Allylic compounds
Asymmetric catalysis
Boron
Hydrogenation
Isomerization
title_short Catalytic regioselective isomerization of 2,2-disubstituted oxetanes to homoallylic alcohols
title_full Catalytic regioselective isomerization of 2,2-disubstituted oxetanes to homoallylic alcohols
title_fullStr Catalytic regioselective isomerization of 2,2-disubstituted oxetanes to homoallylic alcohols
title_full_unstemmed Catalytic regioselective isomerization of 2,2-disubstituted oxetanes to homoallylic alcohols
title_sort Catalytic regioselective isomerization of 2,2-disubstituted oxetanes to homoallylic alcohols
dc.creator.none.fl_str_mv Cabré, Albert|||0000-0003-4367-2635
Rafael, Sergi
Sciortino, Giuseppe|||0000-0001-9657-1788
Ujaque, Gregori|||0000-0001-5896-9998
Verdaguer, Xavier|||0000-0002-9229-969X
Lledós, Agustí|||0000-0001-7909-422X
Riera, Antoni|||0000-0001-7142-7675
author Cabré, Albert|||0000-0003-4367-2635
author_facet Cabré, Albert|||0000-0003-4367-2635
Rafael, Sergi
Sciortino, Giuseppe|||0000-0001-9657-1788
Ujaque, Gregori|||0000-0001-5896-9998
Verdaguer, Xavier|||0000-0002-9229-969X
Lledós, Agustí|||0000-0001-7909-422X
Riera, Antoni|||0000-0001-7142-7675
author_role author
author2 Rafael, Sergi
Sciortino, Giuseppe|||0000-0001-9657-1788
Ujaque, Gregori|||0000-0001-5896-9998
Verdaguer, Xavier|||0000-0002-9229-969X
Lledós, Agustí|||0000-0001-7909-422X
Riera, Antoni|||0000-0001-7142-7675
author2_role author
author
author
author
author
author
dc.subject.none.fl_str_mv Allylic compounds
Asymmetric catalysis
Boron
Hydrogenation
Isomerization
topic Allylic compounds
Asymmetric catalysis
Boron
Hydrogenation
Isomerization
description The selective isomerization of strained heterocyclic compounds is an important tool in organic synthesis. An unprecedented regioselective isomerization of 2,2-disubstituted oxetanes into homoallylic alcohols is described. The use of tris(pentafluorophenyl)borane (B(C6F5)3), a commercially available Lewis acid was key to obtaining good yields and selectivities since other Lewis acids afforded mixtures of isomers and substantial polymerization. The reaction took place under exceptionally mild reaction conditions and very low catalyst loading (0.5 mol %). DFT calculations disclose the mechanistic features of the isomerization and account for the high selectivity displayed by the B(C6F5)3 catalyst. The synthetic applicability of the new reaction is demonstrated by the preparation of γ-chiral alcohols using iridium-catalyzed asymmetric hydrogenation.
publishDate 2020
dc.date.none.fl_str_mv 2
2020-01-01
2020
2020-01-01
dc.type.none.fl_str_mv Article
http://purl.org/coar/resource_type/c_6501
AM
http://purl.org/coar/version/c_ab4af688f83e57aa
dc.type.openaire.fl_str_mv info:eu-repo/semantics/article
format article
dc.identifier.none.fl_str_mv https://ddd.uab.cat/record/279264
https://dx.doi.org/urn:doi:10.1002/anie.201915772
url https://ddd.uab.cat/record/279264
https://dx.doi.org/urn:doi:10.1002/anie.201915772
dc.language.none.fl_str_mv Inglés
eng
language_invalid_str_mv Inglés
language eng
dc.relation.none.fl_str_mv Agencia Estatal de Investigación https://doi.org/10.13039/501100011033 CTQ2017-87840-P
Agencia Estatal de Investigación https://doi.org/10.13039/501100011033 CTQ2017-87889-P
dc.rights.none.fl_str_mv open access
http://purl.org/coar/access_right/c_abf2
https://rightsstatements.org/vocab/InC/1.0/
dc.rights.openaire.fl_str_mv info:eu-repo/semantics/openAccess
rights_invalid_str_mv open access
http://purl.org/coar/access_right/c_abf2
https://rightsstatements.org/vocab/InC/1.0/
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv application/pdf
dc.source.none.fl_str_mv reponame:Dipòsit Digital de Documents de la UAB
instname:Universitat Autònoma de Barcelona
instname_str Universitat Autònoma de Barcelona
reponame_str Dipòsit Digital de Documents de la UAB
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