Quantum Chemical Insight into 1,2-Shift Rearrangement in Bromination of Allylaryls.

ABSTRACT: In this work, we have provided mechanistic insight into the addition of bromine to an allylic double bond of allylaryl derivatives using experimental and DFT-based electronic structure methods. The experimental yields indicate the influence of the functional group on the aryl ring on the ratio of 1,2-dibromo and 1,3-dibromo adducts formed in the reaction. The optimized geometry and the electron density maps of the allylaryls and their cationic intermediates from DFT simulations revealed that electron-rich aryl rings promoted formation of cationic spiro[2.5] intermediate II, whereas electron-poor aryl rings resulted in formation of bromonium intermediate I. It was observed that electron-rich allylaryls promoted the 1,2-shift of the aryl ring that resulted in bond formation bet

SUBMITTER: Hardy D 

PROVIDER: S-EPMC10652718 | biostudies-literature | 2023 Nov

REPOSITORIES: biostudies-literature