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Triarylmethanes and their Medium-Ring Analogues by Unactivated Truce-Smiles Rearrangement of Benzanilides.

ABSTRACT: Intramolecular nucleophilic aromatic substitution (Truce-Smiles rearrangement) of the anions of 2-benzyl benzanilides leads to triarylmethanes in an operationally simple manner. The reaction succeeds even without electronic activation of the ring that plays the role of electrophile in the S_N Ar reaction, being accelerated instead by the preferred conformation imposed by the tertiary amide tether. The amide substituent of the product may be removed or transformed into alternative functional groups. A ring-expanding variant (n to n+4) of the reaction provided a route to doubly benzo-fused medium ring lactams of 10 or 11 members. Hammett analysis returned a ρ value consistent with the operation of a partially concerted reaction mechanism.

SUBMITTER: Abrams R

PROVIDER: S-EPMC8252078 | biostudies-literature | 2021 May

REPOSITORIES: biostudies-literature

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Triarylmethanes and their Medium-Ring Analogues by Unactivated Truce-Smiles Rearrangement of Benzanilides.

Abrams Roman R Jesani Mehul H MH Browning Alex A Clayden Jonathan J

Angewandte Chemie (International ed. in English) 20210408 20

Intramolecular nucleophilic aromatic substitution (Truce-Smiles rearrangement) of the anions of 2-benzyl benzanilides leads to triarylmethanes in an operationally simple manner. The reaction succeeds even without electronic activation of the ring that plays the role of electrophile in the S<sub>N</sub> Ar reaction, being accelerated instead by the preferred conformation imposed by the tertiary amide tether. The amide substituent of the product may be removed or transformed into alternative funct ...[more]

PMID: 33830592

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