13C Kinetic Isotope Effects as a Quantitative Probe To Distinguish between Enol and Enamine Mechanisms in Aminocatalysis

13C Kinetic Isotope Effects as a Quantitative Probe To Distinguish between Enol and Enamine... 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. http://www.deepdyve.com/assets/images/DeepDyve-Logo-lg.png Chemistry - A European Journal Wiley

13C Kinetic Isotope Effects as a Quantitative Probe To Distinguish between Enol and Enamine Mechanisms in Aminocatalysis

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Publisher
Wiley
Copyright
© 2018 Wiley‐VCH Verlag GmbH & Co. KGaA, Weinheim
ISSN
0947-6539
eISSN
1521-3765
D.O.I.
10.1002/chem.201801748
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 JournalWiley

Published: Jan 7, 2018

Keywords: ; ; ; ;

References

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