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- Publisher
- Wiley
- Copyright
- © 2018 Wiley‐VCH Verlag GmbH & Co. KGaA, Weinheim
- ISSN
- 0947-6539
- eISSN
- 1521-3765
- DOI
- 10.1002/chem.201801748
- pmid
- 29654709
- Publisher site
- See Article on Publisher Site
Abstract
A combination of experimental 13C kinetic isotope effects (KIEs) and high‐level density functional theory (DFT) calculations is used to distinguish between “enamine” and “enol” mechanisms in the Michael addition of acetone to trans‐β‐nitrostyrene catalyzed by Jacobsen's primary amine thiourea catalyst. In light of the recent findings that the widely used 18O‐incorporation probe for these mechanisms is flawed, the results described in this communication demonstrate an alternative probe to distinguish between these pathways. A key advantage of this probe is that quantitative mechanistic information is obtained without modifying experimental conditions. This approach is expected to find application in resolving mechanistic debates, while providing valuable information about the key transition state of organocatalyzed reactions involving the α‐functionalization of carbonyls.
Journal
Chemistry - A European Journal – Wiley
Published: Jul 7, 2018
Keywords: ; ; ; ;