Department of Chemistry and Biochemistry, Texas Tech University, Lubbock, TX 79409-1061, USA.
Org Biomol Chem. 2018 Feb 7;16(6):874-879. doi: 10.1039/c7ob02335a.
Thermolysis of a coumarin trichloroacetimidate yields a single rearrangement product. The proposed mechanism is a pseudopericyclic allowed (Woodward-Hoffman forbidden) [3,5]-sigmatropic rearrangement to form the corresponding amide followed by a sigmatropic [1,5]-hydrogen migration. Transition state calculations at the B3LYP/6-31G(d,p) level support this mechanism and suggest the selectivity is influenced by the stability of the intermediates.
香豆素三氯乙酰亚氨酸酯的热解生成单一的重排产物。所提出的机制是一个拟周环允许的（伍德沃德-霍夫曼禁阻的）[3,5]-σ迁移重排，形成相应的酰胺，然后是[1,5]-氢迁移。在 B3LYP/6-31G(d,p)水平的过渡态计算支持这一机制，并表明选择性受中间体稳定性的影响。
