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dc.contributor.author
Grayson, Matthew N.
dc.contributor.author
Pellegrinet, Silvina Carla
dc.contributor.author
Goodman, Jonathan M.
dc.date.available
2020-06-23T18:49:02Z
dc.date.issued
2012-01
dc.identifier.citation
Grayson, Matthew N.; Pellegrinet, Silvina Carla; Goodman, Jonathan M.; Mechanistic insights into the BINOL-derived phosphoric acid-catalyzed asymmetric allylboration of aldehydes; American Chemical Society; Journal of the American Chemical Society; 134; 5; 1-2012; 2716-2722
dc.identifier.issn
0002-7863
dc.identifier.uri
http://hdl.handle.net/11336/107959
dc.description.abstract
BINOL-derived phosphoric acids catalyze the asymmetric allylboration of aldehydes. DFT and QM/MM hybrid calculations showed that the reaction proceeds via a transition state involving both a hydrogen-bonding interaction from the catalyst hydroxyl group to the pseudoaxial oxygen of the cyclic boronate and a stabilizing interaction from the phosphoryl oxygen of the catalyst to the formyl hydrogen of the aldehyde. These interactions lower the energy of the transition structure and provide extra rigidity to the system. This mechanistic pathway is consistent with the experimentally observed enantioselectivity except in one case. We have used our model’s predictions to guide our own experimental work. The conflict is resolved in favor of our calculations.
dc.format
application/pdf
dc.language.iso
eng
dc.publisher
American Chemical Society
dc.rights
info:eu-repo/semantics/openAccess
dc.rights.uri
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
dc.subject
BINOL-DERIVED PHOSPHORIC ACID
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ASYMMETRIC ALLYLBORATION
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CATALYSIS
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Química Orgánica
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Ciencias Químicas
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CIENCIAS NATURALES Y EXACTAS
dc.title
Mechanistic insights into the BINOL-derived phosphoric acid-catalyzed asymmetric allylboration of aldehydes
dc.type
info:eu-repo/semantics/article
dc.type
info:ar-repo/semantics/artículo
dc.type
info:eu-repo/semantics/publishedVersion
dc.date.updated
2020-05-05T13:03:36Z
dc.journal.volume
134
dc.journal.number
5
dc.journal.pagination
2716-2722
dc.journal.pais
Estados Unidos
dc.journal.ciudad
Washington DC
dc.description.fil
Fil: Grayson, Matthew N.. University of Cambridge; Reino Unido
dc.description.fil
Fil: Pellegrinet, Silvina Carla. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina
dc.description.fil
Fil: Goodman, Jonathan M.. University of Cambridge; Reino Unido
dc.journal.title
Journal of the American Chemical Society
dc.relation.alternativeid
info:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/10.1021/ja210200d
dc.relation.alternativeid
info:eu-repo/semantics/altIdentifier/doi/http://dx.doi.org/10.1021/ja210200d
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