Logo do repositório
 
Publicação

Role of 2-Hydroxyimines in Chiral Phosphoric Acid-Catalyzed Mannich-Type Reactions

2026-05-06Artigo científico Acesso aberto
Ver registo simples
dc.contributor.authorHecht, Markus
dc.contributor.authorFischer, Hendrik
dc.contributor.authorSilva, Wagner
dc.contributor.authorEichstetter, Verena
dc.contributor.authorScholtes, Christian L.
dc.contributor.authorFerreira, Ana Sofia
dc.contributor.authorCabrita, Eurico J.
dc.contributor.authorHorinek, Dominik
dc.contributor.authorGschwind, Ruth M.
dc.contributor.institutionUCIBIO - Applied Molecular Biosciences Unit
dc.contributor.pblACS - American Chemical Society
dc.date.accessioned2026-07-14T11:00:02Z
dc.date.available2026-07-14T11:00:02Z
dc.date.issued2026-05-06
dc.descriptionPublisher Copyright: © 2026 The Authors. Published by American Chemical Society.
dc.description.abstractChiral phosphoric acids (CPAs) have emerged as versatile catalysts for asymmetric catalysis, capable of transforming a wide selection of substrates with high stereoselectivities. However, the mechanistic role of higher aggregates in CPA-catalyzed reactions remains poorly understood, although increasing evidence suggests that dimeric and trimeric CPA species can promote challenging transformations. This work provides comprehensive experimental evidence demonstrating that special [CPA/imine]2 species critically enhance the reactivity and selectivity in CPA-catalyzed Mannich-type reactions with imines bearing an N-2-hydroxyphenyl moiety. Using low-temperature NMR spectroscopy, diffusion-ordered spectroscopy (DOSY), and molecular dynamics (MD) simulations, we revealed that imines with a N-2-hydroxyphenyl moiety promote the formation of dimeric [CPA/imine]2 aggregates, while monomeric CPA/imine complexes dominate, with imines lacking this moiety. [CPA/imine]2 formation is favored under low-temperature and high-concentration conditions. Dimers with sufficient structural flexibility provide enhanced reactivity, acidity, and selectivity. In contrast, at higher temperatures, where no [CPA/imine]2 aggregates are formed, the Mannich-type reaction proceeds inefficiently. A nonlinear effect analysis provided evidence of asymmetric amplification in the present Mannich-type reaction, proving the participation of aggregated species in the reaction pathway. Together, these results highlight the importance of controlling catalyst aggregation as a strategy to optimize the reactivity and selectivity in asymmetric organocatalysis.en
dc.description.versionpublishersversion
dc.description.versionpublished
dc.format.extent12
dc.format.extent3843511
dc.identifier.doi10.1021/jacs.5c22497
dc.identifier.issn0002-7863
dc.identifier.otherPURE: 166621757
dc.identifier.otherPURE UUID: 85a2cd74-4dcb-4fad-8caf-3c72ee21d6f8
dc.identifier.otherScopus: 105039267145
dc.identifier.otherPubMed: 42087374
dc.identifier.otherWOS: 001758447000001
dc.identifier.otherPubMedCentral: PMC13195647
dc.identifier.otherORCID: /0000-0001-9381-588X/work/220710114
dc.identifier.urihttp://hdl.handle.net/10362/204493
dc.identifier.urlhttps://www.scopus.com/pages/publications/105039267145
dc.identifier.urlhttps://www.webofscience.com/wos/woscc/full-record/WOS:001758447000001
dc.language.isoeng
dc.peerreviewedyes
dc.subjectCatalysis
dc.subjectBiochemistry
dc.subjectGeneral Chemistry
dc.subjectColloid and Surface Chemistry
dc.titleRole of 2-Hydroxyimines in Chiral Phosphoric Acid-Catalyzed Mannich-Type Reactionsen
dc.title.subtitleEnhancing Reactivity and Selectivity via Dimerizationen
dc.typejournal article
degois.publication.firstPage19598
degois.publication.issue19
degois.publication.lastPage19609
degois.publication.titleJournal of the American Chemical Society
degois.publication.volume148
dspace.entity.typePublication
rcaap.rightsopenAccess

Ficheiros

Principais
A mostrar 1 - 1 de 1
Miniatura
Nome:
Hecht_et_al._2026_..pdf
Tamanho:
3.67 MB
Formato:
Adobe Portable Document Format
Ver/Abrir

Coleções

Home collection (FCT)