α-Hydroxy ketones as masked ester donors in Brønsted base catalyzed conjugate additions to nitroalkenes

Olaizola, Iurre; Campano, Teresa E.; Iriarte, Igor; Vera, Silvia; Mielgo, Antonia; García Castillo, Jesús María; Odriozola Ibarguren, José Manuel; Oiarbide, Mikel; Palomo, Claudio

Publication:
α-Hydroxy ketones as masked ester donors in Brønsted base catalyzed conjugate additions to nitroalkenes

dc.contributor.author	Olaizola, Iurre	es_ES
dc.contributor.author	Campano, Teresa E.	es_ES
dc.contributor.author	Iriarte, Igor	es_ES
dc.contributor.author	Vera, Silvia	es_ES
dc.contributor.author	Mielgo, Antonia	es_ES
dc.contributor.author	García Castillo, Jesús María
dc.contributor.author	Odriozola Ibarguren, José Manuel
dc.contributor.author	Oiarbide, Mikel	es_ES
dc.contributor.author	Palomo, Claudio	es_ES
dc.contributor.department	Institute for Advanced Materials and Mathematics - INAMAT2	en
dc.contributor.department	Química Aplicada	es_ES
dc.contributor.department	Kimika Aplikatua	eu
dc.date.accessioned	2024-01-30T12:15:06Z
dc.date.available	2024-01-30T12:15:06Z
dc.date.issued	2018
dc.date.updated	2024-01-30T12:00:43Z
dc.description.abstract	The catalyst-controlled enantioselective direct addition reaction of enolizable esters and related carboxylic acid derivatives to p electrophiles remains a difficult synthetic transformation. In this study, the suitability of a-hydroxy ketones as ester equivalents capable of being activated by bifunctional Brønsted base catalysts in the context of conjugate addition reactions to nitroolefins is demonstrated. The scope of the reaction, which affords the corresponding Michael adducts with very high stereoselectivity (diastereomeric ratio (d.r.) +95:5, up to 99% enantiomeric excess (ee)), and its limitations are explored, as is the aftermath elaboration of adducts into densely functionalized enantioenriched products.	en
dc.description.abstract	There is now growing evidence that parkinsonism and other extrapyramidal signs are highly prevalent in patients with first-episode psychosis who have never been exposed to antipsychotic drugs. However, the neurocognitive correlates of parkinsonism in this population remained to be clarified. A sample comprising 100 consecutive drug-naive patients with first-episode psychosis were enrolled on the study and followed up for 6 months. Seventy-seven completed assessments at 3 time points (baseline, 1 mo, and 6 mo), involving clinical and cognitive examinations and a specific assessment of motor abnormalities. The Simpson-Angus Scale (SAS) was used for the assessment of extrapyramidal signs, and each motor domain was evaluated with a standard assessment scale. Linear mixed models were built to explore the longitudinal relationships between parkinsonism scores and cognitive impairment. Parkinsonism scores showed significant strong longitudinal associations with deficits in memory, executive functioning, and attention. Spontaneous parkinsonism (total SAS score and hypokinesia and rigidity subscores at baseline) showed high 6-month predictive values for cognitive impairment. In addition, they also had high predictive values for neurologic soft-sign abnormalities but not for dyskinesia, akathisia, and pure catatonic abnormalities. No predictive value was found for glabella-salivation or tremor subscores on the SAS scale. These results emphasize the relevance of the assessment of parkinsonism signs prior to starting to administer antipsychotic drugs, as core manifestations of psychotic illness with a high predictive value for cognitive impairment.	en
dc.description.sponsorship	Support has been provided by the University of the Basque Country UPV/EHU (UFI QOSYC 11/22); the Basque Government (GV grant No IT-628-13); and the Ministerio de Economía y Competitividad (MEC Grant CTQ2016-78487-C2), Spain. I.O. thanks UPV/EHU for a fellowship, and T.C. thanks MEC for a FPI Grant.	en
dc.format.mimetype	application/pdf	en
dc.identifier.citation	Olaizola, I., Campano, T. E., Iriarte, I., Vera, S., Mielgo, A., García, J. M., Odriozola, J. M., Oiarbide, M., & Palomo, C. (2018). Α‐hydroxy ketones as masked ester donors in brønsted base catalyzed conjugate additions to nitroalkenes. Chemistry – A European Journal, 24(15), 3893-3901. https://doi.org/10.1002/chem.201705968	en
dc.identifier.doi	10.1002/chem.201705968
dc.identifier.issn	0947-6539
dc.identifier.uri	https://academica-e.unavarra.es/handle/2454/47253
dc.language.iso	eng	en
dc.publisher	Wiley	en
dc.relation.ispartof	Chemistry - A European Journal 2018, 24, 3893 – 3901	en
dc.relation.projectID	info:eu-repo/grantAgreement/MINECO//CTQ2016-78487-C2	en
dc.relation.publisherversion	https://doi.org/10.1002/chem.201705968
dc.rights	© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim	en
dc.rights.accessRights	Acceso abierto / Sarbide irekia	es
dc.rights.accessRights	info:eu-repo/semantics/openAccess	en
dc.subject	Addition	en
dc.subject	Asymmetric catalysis	en
dc.subject	Esters	en
dc.subject	Organocatalysis	en
dc.subject	Synthesis design	en
dc.title	α-Hydroxy ketones as masked ester donors in Brønsted base catalyzed conjugate additions to nitroalkenes	en
dc.type	Artículo / Artikulua	es
dc.type	info:eu-repo/semantics/article	en
dc.type.version	Versión aceptada / Onetsi den bertsioa	es
dc.type.version	info:eu-repo/semantics/acceptedVersion	en
dspace.entity.type	Publication
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