School of Chemistry, University of Bristol, Cantock's Close, Bristol, BS8 1TS, UK.
Angew Chem Int Ed Engl. 2021 May 10;60(20):11272-11277. doi: 10.1002/anie.202102192. Epub 2021 Apr 8.
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 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.
2-苄基苯甲酰苯胺的阴离子的分子内亲核芳香取代（特鲁斯-斯米尔斯重排）以操作简单的方式生成三芳基甲烷。即使在 S Ar 反应中作为亲电体的环没有电子激活，反应也能成功进行，而是由叔酰胺键合所施加的优先构象加速。产物的酰胺取代基可以被去除或转化为替代的官能团。该反应的环扩大变体（n 到 n+4）为双苯并稠合的 10 或 11 元中环内酰胺提供了一种途径。Hammett 分析得到的 ρ 值与部分协同反应机制的操作一致。
