dc.contributor.author | Roca-López, David | |
dc.contributor.author | Jørgensen, Karl Anker | |
dc.contributor.author | Merino, Pedro | |
dc.contributor.author | Uria Pujana, Uxue ![ORCID](/themes/Mirage2//images/orcid_16x16.png) | |
dc.contributor.author | Reyes Martín, Efraim | |
dc.contributor.author | Carrillo Fernández, María Luisa ![ORCID](/themes/Mirage2//images/orcid_16x16.png) | |
dc.contributor.author | Vicario Hernando, José Luis ![ORCID](/themes/Mirage2//images/orcid_16x16.png) | |
dc.date.accessioned | 2017-10-31T13:39:13Z | |
dc.date.available | 2017-10-31T13:39:13Z | |
dc.date.issued | 2016 | |
dc.identifier.citation | Chemistry - A European Journal 22(3) : 884 – 889 (2016) | es_ES |
dc.identifier.issn | 1521-3765 | |
dc.identifier.uri | http://hdl.handle.net/10810/23267 | |
dc.description.abstract | The modes of catalytic action of three squaramide-derived
bifunctional organocatalysts have been investigated using DFT
methods. The [5+2] cycloaddition between oxidopyrilium ylides and
enals has been used as model reaction. Two primary modes are
possible for the different catalysts studied. The preference for one
mode over the other is due to the possibility of additional favourable
π,π-interactions between the H-bond activated pyrilium ylide and an
electron-deficient aromatic ring bonded to a squaramide NH-group.
The model can be extended to other reactions catalyzed by the
same catalysts such as formal [2+2] cycloadditions between
nitroalkenes and α,β-unsaturated aldehydes. The computational
results are in excellent concurrence with the available experimental
reports on the observed total enantioselectivity and differences in
diastereoselectivity depending on the substrate and the reaction | es_ES |
dc.description.sponsorship | This work was supported by Spanish MINECO Contracts CTQ2013-44367-C2-1-P (to P.M.) and CTQ2014-52107 (to J.L.V.). We also acknowledge the Government of Aragón (Spain) (Group E-10), the Basque Government (Spain) (IT328-10) and Aarhus University (Denmark) for financial support. We acknowledge the Institute of Biocomputation and Physics of Complex Systems (BIFI) at the University of Zaragoza (Spain) for computer time at clusters Terminus and Memento. D.R.-L. Thanks the Spanish Ministry of Education (MEC) for a predoctoral grant (FPU program). | es_ES |
dc.language.iso | eng | es_ES |
dc.publisher | Wiley-VCH | es_ES |
dc.relation | info:eu-repo/grantAgreement/MINECO/CTQ2013-44367-C2-1-P | es_ES |
dc.relation | info:eu-repo/grantAgreement/MINECO/CTQ2014-52107 | es_ES |
dc.rights | info:eu-repo/semantics/openAccess | es_ES |
dc.subject | asymmetric catalysis | es_ES |
dc.subject | density functional | es_ES |
dc.subject | calculations | es_ES |
dc.subject | dienamines | es_ES |
dc.subject | hydrogen bonds | es_ES |
dc.subject | pi interactions | es_ES |
dc.title | Mechanistic Insights in the Mode of Action of Bifunctional Pyrrolidine-Squaramide-derived Organocatalysts | es_ES |
dc.type | info:eu-repo/semantics/article | es_ES |
dc.rights.holder | © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim | es_ES |
dc.relation.publisherversion | http://onlinelibrary.wiley.com/doi/10.1002/chem.201504705/abstract | es_ES |
dc.departamentoes | Química orgánica II | es_ES |
dc.departamentoeu | Kimika organikoa II | es_ES |