To derive a highly strained PAH, we conducted a sequential procedure: organic synthesis of a PAH with two azuleno moieties in proximity to each other—that is, DAPh 1 —and thermal cyclodehydroganation of the molecule 1 adsorbed onto a Cu surface. The product DAPyr 4 adopts a planar configuration on the surface, in spite of the fact that the azuleno moieties are sterically hindered by further mutual proximity.
Therefore, the azuleno moieties flattened on the surface are highly strained. In order to eliminate the local strain instability, the molecule 4 is thermally induced to react predominantly into an intrinsically flat PAH with a fulvaleno moiety, which has never been yielded by conventional organic synthesis.
The importance of the strain for the skeletal rearrangement is reinforced by the observation that a reference molecule—DAA 2 —exhibits no thermal reactivity at the surface because it cannot eliminate the strain by any skeletal rearrangement. Such strain-induced reactions of organic molecules on surfaces would be a useful approach to synthesizing functional chemical products. The details of the calculations are described in Supplementary Methods. The data that support the findings of this study are available from the corresponding author on reasonable request.
How to cite this article: Shiotari, A.
Strain-induced skeletal rearrangement of a polycyclic aromatic hydrocarbon on a copper surface. Wiberg, K. The concept of strain in organic chemistry.
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