Enantioselective Ring-Opening Polymerization of rac-Lactide Dictated by Densely Substituted Aminoacids

Organocatalysis is becoming an important tool in polymer science because of its versatility and specificity. To date a limited number of organic catalysts have demonstrated the ability to promote stereocontrolled polymerizations. In this work we report one of the first examples of chirality transfer...

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Autores: Sánchez Sánchez, Ana, Rivilla de la Cruz, Iván, Agirre, Maddalen, Basterrechea Gorostiza, Andere, Etxeberria Lizarraga, Agustín, Veloso Fernández, Antonio, Sardon Muguruza, Haritz, Mecerreyes Molero, David, Cossío Mora, Fernando Pedro
Formato: artículo
Fecha de publicación:2017
País:España
Recursos:Universidad del País Vasco
Repositorio:Addi. Archivo Digital para la Docencia y la Investigación
OAI Identifier:oai:addi.ehu.eus:10810/31650
Acesso em linha:http://hdl.handle.net/10810/31650
Access Level:acceso abierto
Palavra-chave:enantioselective
ring opening
organocatalysis
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spelling Enantioselective Ring-Opening Polymerization of rac-Lactide Dictated by Densely Substituted AminoacidsSánchez Sánchez, AnaRivilla de la Cruz, IvánAgirre, MaddalenBasterrechea Gorostiza, AndereEtxeberria Lizarraga, AgustínVeloso Fernández, AntonioSardon Muguruza, HaritzMecerreyes Molero, DavidCossío Mora, Fernando Pedroenantioselectivering openingorganocatalysisOrganocatalysis is becoming an important tool in polymer science because of its versatility and specificity. To date a limited number of organic catalysts have demonstrated the ability to promote stereocontrolled polymerizations. In this work we report one of the first examples of chirality transfer from a catalyst to a polymer in the organocatalyzed ring-opening polymerization (ROP) of rac-lactide (rac-LA). We have polymerized rac-LA using the diastereomeric densely substituted amino acids (2S,3R,4S,5S)-1-methyl-4-nitro-3,5-diphenylpyrrolidine- 2-carboxylic acid (endo-6) and (2S,3S,4R,5S)-1-methyl-4- nitro-3,5-diphenylpyrrolidine-2-carboxylic acid (exo-6), combined with 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) as a cocatalyst. Both diastereoisomers not only showed the ability to synthesize enriched isotactic polylactide with a Pm higher than 0.90 at room temperature but also were able to preferentially promote the polymerization of one of the isomers (L or D) with respect to the other. Thus, exo-6 preferentially polymerized Llactide, whereas endo-6 preferred D-lactide as the substrate. Density functional theory calculations were conducted to investigate the origins of this unique stereocontrol in the polymerization, providing mechanistic insight and explaining why the chirality of the catalyst is able to define the stereochemistry of the monomer insertion.Financial support of this research by the MINECO (CTQ2016-80375-P, Consolider CTQ2016-81797-REDC, SUSPOL, and FDI 16507), the Gobierno Vasco/Eusko Jaurlaritza (Grants IT673-13 and IT618-13), the University of the Basque Country UPV/EHU (UFI 11/22 QOSYC), and the European Commission (SUPSOL-EJD 642671) is gratefully acknowledged. A.S.-S. is thankful for the Postdoctoral Funding for Doctoral Research Staff Improvement Grant from the Basque Government.ACSEuropean Commission201920192017info:eu-repo/semantics/articleapplication/pdfhttp://hdl.handle.net/10810/31650reponame:Addi. Archivo Digital para la Docencia y la Investigacióninstname:Universidad del País VascoInglésinfo:eu-repo/grantAgreement/EC/H2020/642671info:eu-repo/grantAgreement/MINECO/CTQ2016-80375-P/info:eu-repo/grantAgreement/MINECO/CTQ2016-81797-REDC/https://pubs.acs.org/doi/10.1021/jacs.6b13080info:eu-repo/semantics/openAccess(c) 2017 American Chemical Societyoai:addi.ehu.eus:10810/316502026-06-18T09:23:17Z
dc.title.none.fl_str_mv Enantioselective Ring-Opening Polymerization of rac-Lactide Dictated by Densely Substituted Aminoacids
title Enantioselective Ring-Opening Polymerization of rac-Lactide Dictated by Densely Substituted Aminoacids
spellingShingle Enantioselective Ring-Opening Polymerization of rac-Lactide Dictated by Densely Substituted Aminoacids
Sánchez Sánchez, Ana
enantioselective
ring opening
organocatalysis
title_short Enantioselective Ring-Opening Polymerization of rac-Lactide Dictated by Densely Substituted Aminoacids
title_full Enantioselective Ring-Opening Polymerization of rac-Lactide Dictated by Densely Substituted Aminoacids
title_fullStr Enantioselective Ring-Opening Polymerization of rac-Lactide Dictated by Densely Substituted Aminoacids
title_full_unstemmed Enantioselective Ring-Opening Polymerization of rac-Lactide Dictated by Densely Substituted Aminoacids
title_sort Enantioselective Ring-Opening Polymerization of rac-Lactide Dictated by Densely Substituted Aminoacids
dc.creator.none.fl_str_mv Sánchez Sánchez, Ana
Rivilla de la Cruz, Iván
Agirre, Maddalen
Basterrechea Gorostiza, Andere
Etxeberria Lizarraga, Agustín
Veloso Fernández, Antonio
Sardon Muguruza, Haritz
Mecerreyes Molero, David
Cossío Mora, Fernando Pedro
author Sánchez Sánchez, Ana
author_facet Sánchez Sánchez, Ana
Rivilla de la Cruz, Iván
Agirre, Maddalen
Basterrechea Gorostiza, Andere
Etxeberria Lizarraga, Agustín
Veloso Fernández, Antonio
Sardon Muguruza, Haritz
Mecerreyes Molero, David
Cossío Mora, Fernando Pedro
author_role author
author2 Rivilla de la Cruz, Iván
Agirre, Maddalen
Basterrechea Gorostiza, Andere
Etxeberria Lizarraga, Agustín
Veloso Fernández, Antonio
Sardon Muguruza, Haritz
Mecerreyes Molero, David
Cossío Mora, Fernando Pedro
author2_role author
author
author
author
author
author
author
author
dc.contributor.none.fl_str_mv European Commission
dc.subject.none.fl_str_mv enantioselective
ring opening
organocatalysis
topic enantioselective
ring opening
organocatalysis
description Organocatalysis is becoming an important tool in polymer science because of its versatility and specificity. To date a limited number of organic catalysts have demonstrated the ability to promote stereocontrolled polymerizations. In this work we report one of the first examples of chirality transfer from a catalyst to a polymer in the organocatalyzed ring-opening polymerization (ROP) of rac-lactide (rac-LA). We have polymerized rac-LA using the diastereomeric densely substituted amino acids (2S,3R,4S,5S)-1-methyl-4-nitro-3,5-diphenylpyrrolidine- 2-carboxylic acid (endo-6) and (2S,3S,4R,5S)-1-methyl-4- nitro-3,5-diphenylpyrrolidine-2-carboxylic acid (exo-6), combined with 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) as a cocatalyst. Both diastereoisomers not only showed the ability to synthesize enriched isotactic polylactide with a Pm higher than 0.90 at room temperature but also were able to preferentially promote the polymerization of one of the isomers (L or D) with respect to the other. Thus, exo-6 preferentially polymerized Llactide, whereas endo-6 preferred D-lactide as the substrate. Density functional theory calculations were conducted to investigate the origins of this unique stereocontrol in the polymerization, providing mechanistic insight and explaining why the chirality of the catalyst is able to define the stereochemistry of the monomer insertion.
publishDate 2017
dc.date.none.fl_str_mv 2017
2019
2019
dc.type.none.fl_str_mv info:eu-repo/semantics/article
format article
dc.identifier.none.fl_str_mv http://hdl.handle.net/10810/31650
url http://hdl.handle.net/10810/31650
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv info:eu-repo/grantAgreement/EC/H2020/642671
info:eu-repo/grantAgreement/MINECO/CTQ2016-80375-P/
info:eu-repo/grantAgreement/MINECO/CTQ2016-81797-REDC/
https://pubs.acs.org/doi/10.1021/jacs.6b13080
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
(c) 2017 American Chemical Society
eu_rights_str_mv openAccess
rights_invalid_str_mv (c) 2017 American Chemical Society
dc.format.none.fl_str_mv application/pdf
dc.publisher.none.fl_str_mv ACS
publisher.none.fl_str_mv ACS
dc.source.none.fl_str_mv reponame:Addi. Archivo Digital para la Docencia y la Investigación
instname:Universidad del País Vasco
instname_str Universidad del País Vasco
reponame_str Addi. Archivo Digital para la Docencia y la Investigación
collection Addi. Archivo Digital para la Docencia y la Investigación
repository.name.fl_str_mv
repository.mail.fl_str_mv
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score 15,301629

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