Understanding sulfone behavior in palladium-catalyzed domino reactions with aryl iodides |
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Authors: | Alonso Inés Alcamí Manuel Mauleón Pablo Carretero Juan C |
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Affiliation: | Departamento de Química Orgánica, Facultad de Ciencias, Universidad Autónoma de Madrid, Cantoblanco 28049 Madrid, Spain. ines.alonso@uam.es |
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Abstract: | Unlike traditionally used acyclic 1,2-disubstituted alkenes, the reaction of alpha,beta-unsaturated phenyl sulfones with aryl iodides under Heck reaction conditions takes place mainly by means of a four-component domino process, involving one unit of the alkene and three units of the aryl iodide, affording substituted 9-phenylsulfonyl-9,10-dihydrophenanthrenes. We report here the results of a computational study on the mechanism of this domino arylation reaction. Based on these results we can explain why vinyl sulfones, unlike other electron-deficient alkenes such as enones, preferentially follow this domino pathway instead of the usual Heck pathway. The key step is a C-H activation process in which a five-membered palladacycle is formed. The greater ability of vinyl sulfones, relative to enones, to reach the transition state that leads to the formation of the initial palladacycle makes the difference. |
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Keywords: | C?H activation density functional calculations domino reactions Heck reaction sulfones |
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