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Article Dans Une Revue Chemistry - A European Journal Année : 2015

Azaphilic versus Carbophilic Coupling at C=N Bonds: Key Steps in Titanium-Assisted Multicomponent Reactions

Résumé

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.

Dates et versions

hal-01241045 , version 1 (09-12-2015)

Identifiants

Citer

Torsten Roth, Hubert Wadepohl, Eric Clot, Lutz H. Gade. Azaphilic versus Carbophilic Coupling at C=N Bonds: Key Steps in Titanium-Assisted Multicomponent Reactions. Chemistry - A European Journal, 2015, 21 (18730–18738), ⟨10.1002/chem.201503732⟩. ⟨hal-01241045⟩
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