Brønsted-Acid-Catalyzed Intramolecular Carbonyl–Olefin Reactions: Interrupted Metathesis vs Carbonyl-Ene ReactionClick to copy article linkArticle link copied!
- Tanmay MalakarTanmay MalakarDepartment of Chemistry, University of Michigan, 930 North University Avenue, Ann Arbor, Michigan 48109, United StatesMore by Tanmay Malakar
- Paul M. Zimmerman*Paul M. Zimmerman*Email: [email protected]Department of Chemistry, University of Michigan, 930 North University Avenue, Ann Arbor, Michigan 48109, United StatesMore by Paul M. Zimmerman
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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