Cross-dehydrogenative coupling (CDC) reactions have attracted attention as short-step synthetic methods for C–C bond formation. Recently, we have developed CDC reactions between naphthalene and fluorobenzene. Rather than exhibiting general regioselectivity, this reaction proceeds selectively at the β-position of naphthalene. In this study, investigation using model complexes as reaction intermediates revealed that the origin of the unique selectivity is the exclusive occurrence of reductive elimination at the β-position. Detailed studies on the reductive elimination showed that the steric hindrance of the naphthyl group and the electron-withdrawing properties of fluorobenzene determine the position at which the reductive elimination reaction proceeds. These results show that the selectivity of the C–H functionalisation of polycyclic aromatic hydrocarbons (PAHs) is determined not by the C–H cleavage step, but by the subsequent reductive elimination step. The regioselective CDC reaction was adaptable to various PAHs but was less selective for pyrene with extended π-conjugation. In fluorobenzene substrates, the F atoms at the two ortho positions of the C–H moiety are necessary for high selectivity. The substrate ranges are in good agreement with the proposed mechanism, in which the reductive elimination step determines the regioselectivity.
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