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13 C Kinetic Isotope Effects as a Quantitative Probe To Distinguish between Enol and Enamine Mechanisms in Aminocatalysis
Author(s) -
Roytman Vladislav A.,
Karugu Rachael W.,
Hong Yun,
Hirschi Jennifer S.,
Vetticatt Mathew J.
Publication year - 2018
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201801748
Subject(s) - enamine , kinetic isotope effect , chemistry , enol , thiourea , amine gas treating , catalysis , density functional theory , computational chemistry , transition state , organic chemistry , deuterium , physics , quantum mechanics
A combination of experimental 13 C 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 18 O‐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.