ArticleThe Journal of organic chemistry2021
Brønsted-Acid-Catalyzed Intramolecular Carbonyl-Olefin Reactions: Interrupted Metathesis vs Carbonyl-Ene Reaction.
Article in The Journal of organic chemistry, 2021. The graph could read no effect estimate from its abstract, so it casts no vote on the map. Cited by 3 papers.
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Who cites it
3 citing papers in PubMed.
- Hydrogen Bonding Networks Enable Brønsted Acid-Catalyzed Carbonyl-Olefin Metathesis.Angewandte Chemie (International ed. in English) · 2022Article
- Autonomous Reaction Network Exploration in Homogeneous and Heterogeneous Catalysis.Topics in catalysis · 2022Article
- The Catalytic Asymmetric Intermolecular Prins Reaction.Journal of the American Chemical Society · 2021Article
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2 authors.
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Abstract
Lewis acid catalysts have been shown to promote carbonyl-olefin metathesis through a critical four-membered-ring oxetane intermediate. Recently, Brønsted-acid catalysis of related substrates was similarly proposed to result in a transient oxetane, which fragments within a single elementary step via a postulated oxygen-atom transfer mechanism. Herein, careful quantum chemical investigations show that Brønsted acid (triflic acid, TfOH) instead invokes a mechanistic switch to a carbonyl-ene reaction, and oxygen-atom transfer is uncompetitive. TfOH's conjugate base is also found to rearrange H atoms and allow isomerization of the carbocations that appear after the carbonyl-ene reaction. The mechanism explains available experimental information, including the skipped diene species that appear transiently before product formation. The present study clarifies the mechanism for activation of intramolecular carbonyl-olefin substrates by Brønsted acids and provides important insights that will help develop this exciting class of catalysts.
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