Toward the Rebirth of Aromatic Cope Rearrangement – ArCopeRebirth

The Aromatic Cope Rearrangement (ArCopeR) is a challenging transformation that has been the subject to very few studies considering the huge thermodynamic and kinetic predicaments inherent to this transformation. However, the ArCopeR could be a useful and environmentally benign transformation (i.e. atom economy, traceless activation…) to reach two important challenges in modern synthetic chemistry. Firstly, because the entire process allows site-specific allylation of an (hetero-)aromatic which is a new route for what is called C-H activation. Secondly if the ArCopeR is interrupted, the [3,3] sigmatropic reaction allows a dearomatisation which is an innovative access to structurally diverse three-dimensional polycyclic molecules. With ArCopeRebirth project, we propose to take the ArCopeR out of a confidential area of research mostly based on an unexpected reactivity and push it in the modern synthetic toolbox that can be efficiently implemented in rational synthesis of complex molecular architectures. A first field of investigation will be the search of effective methodologies using both organic and gold catalysis for the construction of a wide range of complex chiral molecules embedded a 1,5-hexadiene scaffold, starting materials of the ArCopeR. Extensive studies of relevant thermal dearomatisation and CH-functionalisation by interrupted and normal ArCopeR will be a cornerstone of the project. Moreover, new strategies based on gold catalysis will be investigated to lowering rearrangement barriers and/or change the reaction pathway to compete with the classic sigmatropic concerted process. All along the project, mechanistic investigation by experimental studies & quantum mechanics (QM) calculations will be carried out to fully understand the discovered processes and allow new breakthrough.