Development of the titanium–TADDOLate-catalyzed asymmetric fluorination of β-ketoesters
Open access
Datum
2011-10-17Typ
- Journal Article
ETH Bibliographie
yes
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Abstract
Titanium-based Lewis acids catalyze the α-fluorination of β-ketoesters by electrophilic N–F-fluorinating reagents. Asymmetric catalysis with TADDOLato–titanium(IV) dichloride (TADDOL = α,α,α',α'-tetraaryl-(1,3-dioxolane-4,5-diyl)-dimethanol) Lewis acids produces enantiomerically enriched α-fluorinated β-ketoesters in up to 91% enantiomeric excess, with either F–TEDA (1-chloromethyl-4-fluoro-1,4-diazoniabicyclo[2.2.2]octane bis(tetrafluoroborate)) in acetonitrile solution or NFSI (N-fluorobenzenesulfonimide) in dichloromethane solution as fluorinating reagents. The effects of various reaction parameters and of the TADDOL ligand structure on the catalytic activity and enantioselectivity were investigated. The absolute configuration of several fluorination products was assigned through correlation. Evidence for ionization of the catalyst complex by chloride dissociation, followed by generation of titanium β-ketoenolates as key reaction intermediates, was obtained. Based on the experimental findings, a general mechanistic sketch and a steric model of induction are proposed. Mehr anzeigen
Persistenter Link
https://doi.org/10.3929/ethz-b-000160437Publikationsstatus
publishedExterne Links
Zeitschrift / Serie
Beilstein Journal of Organic ChemistryBand
Seiten / Artikelnummer
Verlag
Beilstein-Institut zur Förderung der Chemischen WissenschaftenThema
Asymmetric catalysis; Fluorination; Fluoroorganic compounds; TADDOL; TitaniumOrganisationseinheit
03363 - Togni, Antonio (emeritus) / Togni, Antonio (emeritus)
ETH Bibliographie
yes
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