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

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 SNAr 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 rho value consistent with the operation of a partially concerted reaction mechanism.

Automated summary

Intramolecular nucleophilic aromatic substitution of the anions of 2-benzyl benzanilides leads to triarylmethanes in an operationally simple manner. The reaction can proceed without electronic activation of the ring, instead being accelerated by the preferred conformation imposed by the tertiary amide tether. Additionally, a ring-expanding variant of the reaction provides a route to doubly benzo-fused medium ring lactams of 10 or 11 members.