The Danheiser benzannulation is a regiocontrolled phenol annulation. This annulation provides an efficient route to form an aromatic ring in one step. It is a thermal combination of a substituted cyclobutenones with heterosubstituted acetylenes to produce highly substituted aromatic compounds, specifically phenols or resorcinols (Scheme 1). This benzannulation reaction creates previously unaccessed aromatic substitution patterns. A variety of substituted aromatic rings can be prepared using this method including: phenols, naphthalenes, benzofurans, benzothiophenes, indoles, and carbazoles.
The modified Danheiser benzannulation allows the synthesis of polycyclic aromatic and heteroaromatic systems. This also includes napthalenes, benzofurans and indoles. This second generation aromatic annulation is achieved by irradiation of a solution of acetylene and a vinyl or aryl α-diazo ketone in dichloroethane. This reaction utilizes the photochemical Wolff rearrangement of a diazoketone to generate an aryl or vinylketene. These ketene intermediates cannot be isolated due to their high reactivity to form diketenes. These rearrangements are performed in the presence of unsaturated compounds which undergo [2+2] cycloadditions with the in situ generated ketenes. When ketenes are formed in the presence of alkynes they proceed through pericyclic reactions to generate a substituted aromatic ring (Scheme 2). Avoiding the use of the high energy cyclobutenone starting materials provides access to a wider variety of substituted aromatic compounds.
This reaction is quite complementary to the Wulff–Dötz reaction. This is a [2+1] cycloaddition of a carbene to an alkyne or alkene (more specifically in the Dӧtz reaction a carbene coordinated to a metal carbonyl group) to produce substituted aromatic phenols.