dc.contributor.author | Sánchez Sánchez, Ana | |
dc.contributor.author | Rivilla de la Cruz, Iván | |
dc.contributor.author | Agirre, Maddalen | |
dc.contributor.author | Basterrechea Gorostiza, Andere | |
dc.contributor.author | Etxeberria Lizarraga, Agustín | |
dc.contributor.author | Veloso Fernández, Antonio | |
dc.contributor.author | Sardon Muguruza, Haritz | |
dc.contributor.author | Mecerreyes Molero, David | |
dc.contributor.author | Cossío Mora, Fernando Pedro | |
dc.date.accessioned | 2019-02-21T18:19:43Z | |
dc.date.available | 2019-02-21T18:19:43Z | |
dc.date.issued | 2017-03-08 | |
dc.identifier.citation | Journal of the American Chemical Society 139(13) : 4805−4814 (2017) | es_ES |
dc.identifier.issn | 0002-7863 | |
dc.identifier.uri | http://hdl.handle.net/10810/31650 | |
dc.description.abstract | 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. | es_ES |
dc.description.sponsorship | 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. | es_ES |
dc.language.iso | eng | es_ES |
dc.publisher | ACS | es_ES |
dc.relation | info:eu-repo/grantAgreement/EC/H2020/642671 | es_ES |
dc.relation | info:eu-repo/grantAgreement/MINECO/CTQ2016-80375-P | es_ES |
dc.relation | info:eu-repo/grantAgreement/MINECO/CTQ2016-81797-REDC | es_ES |
dc.rights | info:eu-repo/semantics/openAccess | es_ES |
dc.subject | enantioselective | es_ES |
dc.subject | ring opening | es_ES |
dc.subject | organocatalysis | es_ES |
dc.title | Enantioselective Ring-Opening Polymerization of rac-Lactide Dictated by Densely Substituted Aminoacids | es_ES |
dc.type | info:eu-repo/semantics/article | es_ES |
dc.rights.holder | (c) 2017 American Chemical Society | es_ES |
dc.relation.publisherversion | https://pubs.acs.org/doi/10.1021/jacs.6b13080 | es_ES |
dc.identifier.doi | 10.1021/jacs.6b13080 | |
dc.contributor.funder | European Commission | |
dc.departamentoes | Ciencia y tecnología de polímeros | es_ES |
dc.departamentoeu | Polimeroen zientzia eta teknologia | es_ES |