CE07 - Chimie moléculaire

Toward the Rebirth of Aromatic Cope Rearrangement – ArCopeRebirth

Submission summary

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.

Project coordination

Emmanuel RIGUET (Institut de Chimie Moléculaire de Reims)

The author of this summary is the project coordinator, who is responsible for the content of this summary. The ANR declines any responsibility as for its contents.

Partner

IC Université Strasbourg
ICMR Institut de Chimie Moléculaire de Reims

Help of the ANR 434,717 euros
Beginning and duration of the scientific project: September 2022 - 48 Months

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