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Updated: Apr 16, 2026

Microwave-assisted Intramolecular Dehydrogenative Diels-Alder Reactions for the Synthesis of Functionalized Naphthalenes/Solvatochromic Dyes
Published on: April 1, 2013
A Diels-Alder reaction triggered by a [4 + 3] metallacycloaddition
Ángela Vivancos1, Florencia Vattier1, Joaquín López-Serrano1
1Instituto de Investigaciones Químicas, Departamento de Química Inorgánica, and Centro de Innovación en Química Avanzada, Consejo Superior de Investigaciones Científicas and Universidad de Sevilla, Av. Amírico Vespucio 49, 41092 Sevilla, Spain.
Abstract:
The Tp(Me2)Ir(III) complex 1-OH2 (Tp(Me2) = hydrotris(3,5-dimethylpyrazolyl)borate), which contains a labile molecule of water and an iridium-bonded alkenyl moiety (-C(R)═C(R)-(R=CO2Me)) as part of a benzo-annulated five-membered iridacycle, reacts readily with the conjugated dienes butadiene and 2,3-dimethylbutadiene to afford the corresponding Diels-Alder products. Experimental and DFT studies are in accordance with an initial [4 + 3] cyclometalation reaction between the diene and the five-coordinated 16-electron organometallic fragment 1 (generated from 1-OH2 by facile water dissociation). The reaction can be extended to a related TpIr(III) complex (Tp = hydrotris(pyrazolyl)borate) that also features a labile ligand (i.e., 2-THF).
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Conformation
The simplest example of a diene is 1,3-butadiene, an acyclic conjugated π system. At room temperature, the molecule exists as a mixture of s-cis and s-trans conformers by virtue of rotation around the carbon–carbon single bond. Although the s-trans isomer is...