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

M. Elena De Orbe, Laura Amenós, Mariia S. Kirillova, Yahui Wang, Verónica López-Carrillo, Feliu Maseras, Antonio M. Echavarren

Research output: Contribution to journalArticleResearchpeer-review

35 Citations (Scopus)

Abstract

© 2017 American Chemical Society. 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.
Original languageEnglish
Pages (from-to)10302-10311
JournalJournal of the American Chemical Society
Volume139
Issue number30
DOIs
Publication statusPublished - 2 Aug 2017

Fingerprint Dive into the research topics of 'Cyclobutene vs 1,3-Diene Formation in the Gold-Catalyzed Reaction of Alkynes with Alkenes: The Complete Mechanistic Picture'. Together they form a unique fingerprint.

Cite this