Azaphilic versus carbophilic coupling at C=N bonds

• Verfasst von: Roth, Torsten [VerfasserIn]
• Verfasst von: Wadepohl, Hubert [VerfasserIn]
• Verfasst von: Clot, Eric [VerfasserIn]
• Verfasst von: Gade, Lutz H. [VerfasserIn]
• Titel: Azaphilic versus carbophilic coupling at C=N bonds
• Titelzusatz: key steps in titanium-assisted multicomponent reactions
• Verf.angabe: Torsten Roth, Hubert Wadepohl, Eric Clot, and Lutz H. Gade
• E-Jahr: 2015
• Jahr: [2015]
• Umfang: 9 S.
• Illustrationen: Illustrationen
• Fussnoten: Gesehen am 08.07.2020
• Titel Quelle: Enthalten in: Chemistry - a European journal
• Ort Quelle: Weinheim : Wiley-VCH, 1995
• Jahr Quelle: 2015
• Band/Heft Quelle: 21(2015), 51, Seite 18730-18738
• ISSN Quelle: 1521-3765
• DOI: doi:10.1002/chem.201503732
• Datenträger: Online-Ressource
• Sprache: eng
• Sach-SW: heterocycles
• Sach-SW: metallacycles
• Sach-SW: multicomponent reactions
• Sach-SW: synthetic methods
• Sach-SW: titanium
• K10plus-PPN: 1713916010

Abstract

Abstract Consecutive C- and N-arylation of N-heterocyclic nitriles is mediated by titanium(IV) alkoxides. The carbo- and azaphilic arylation step may be separated by choosing the order in which the two equivalents of aryl transfer reagent are added. In the course of this transformation, the ancillary N-heterocycle acts as both a directing anchor group and electron reservoir. In the selectivity-determining step, the selectivity is governed by a choice between (direct) C- and Ti-arylation; the latter opens up a reaction pathway that allows further migration to the nitrogen atom. The isolation of metal-containing aggregates from the reaction mixture and computational studies gave insights into the reaction mechanism. Subsequently, a multicomponent one-pot protocol was devised to rapidly access complex quaternary carbon centers.