The Photo-Dehydro-Diels-Alder Reaction: An Efficient Route to Naphthalenes

Abstract

The photo-dehydro-Diels-Alder reaction (PDDA), a new photochemical route to naphthalenes is presented. The [4+2] cycloaddition takes place between 3-arylynones and arylacetylenes, in which these moieties may be located in two molecules (intermolecular PDDA, 1) or in the same molecule (intramolecular PDDA, 5 and 9). Especially the latter approach is attractive from a preparative point of view and permits a straightforward access to highly functionalized naphthalenes. The irradiation of unsymmetrical reactants 9 provides, in contrast to symmetrical reactants 5, two isomeric naphthalenes. We found that the regioselectivity can be easily influenced by suitably located substituents in the aromatic rings and by blocking undesired positions. Notably, the PDDA may be used for the preparation of binaphthyls, as shown by the formation of 14 and 16. The mechanism of the PDDA was elucidated by spectroscopic analyses and theoretical (DFT) calculations.

dehydro Diels-Alder reaction - naphthalenes - binaphthyls - photocyclization

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