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

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.

SUBMITTER: Roth T

PROVIDER: S-EPMC4832833 | biostudies-other | 2015 Dec

REPOSITORIES: biostudies-other

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

Roth Torsten T Wadepohl Hubert H Clot Eric E Gade Lutz H LH

Chemistry (Weinheim an der Bergstrasse, Germany) 20151106 51

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 ...[more]

PMID: 26542982

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