Autor/a:
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de Orbe, M. Elena; Amenós, Laura; Kirillova, Mariia S.; Wang, Yahui; Loṕez-Carrillo, Verónica; Maseras, Feliu; Echavarren, Antonio M.
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Abstract:
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The intermolecular gold(I)-catalyzed reaction
between arylalkynes and alkenes leads to cyclobutenes by a [2 +
2] cycloaddition, which takes place stepwise, first by formation
of cyclopropyl gold(I) carbenes, followed by a ring expansion.
However, 1,3-butadienes are also formed in the case of ortho-
substituted arylalkynes by a metathesis-type process. The
corresponding reaction of alkenes with aryl-1,3-butadiynes,
ethynylogous to arylalkynes, leads exclusively to cyclobutenes.
A comprehensive mechanism for the gold(I)-catalyzed reaction
of alkynes with alkenes is proposed on the basis of density
functional theory calculations, which shows that the two pathways leading to cyclobutenes or dienes are very close in energy. The key intermediates are cyclopropyl gold(I) carbenes, which have been independently generated by retro-Buchner reaction from stereodefined 1a,7b-dihydro-1H-cyclopropa[a]naphthalenes. |