Cyclobutene vs 1,3-Diene Formation in the Gold-Catalyzed Reaction of Alkynes with Alkenes: The Complete Mechanistic Picture

• Published in: Journal of the American Chemical Society Vol. 139; no. 30; pp. 10302 - 10311
• Main Authors: de Orbe, M. Elena, Amenós, Laura, Kirillova, Mariia S, Wang, Yahui, López-Carrillo, Verónica, Maseras, Feliu, Echavarren, Antonio M
• Format: Journal Article
• Language: English
• Published: WASHINGTON American Chemical Society 02.08.2017; Amer Chemical Soc
• Subjects: Chemistry; Chemistry, Multidisciplinary; Physical Sciences; Science & Technology; ORGANIC-SYNTHESIS; 1,6-ENYNES; INTERMOLECULAR 2+2 CYCLOADDITION; BICYCLIC ALKENES; II CYCLOISOMERIZATION; TERMINAL ALKYNES; SKELETAL REARRANGEMENT; DERIVATIVES; ENYNES; STRATEGIES
• ISSN: 0002-7863; 1520-5126
• DOI: 10.1021/jacs.7b03005

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.