Report for: Isotope Effects Reveal the Mechanism of Enamine Formation in l -Proline-Catalyzed α-Amination of Aldehydes

Title	Isotope Effects Reveal the Mechanism of Enamine Formation in l -Proline-Catalyzed α-Amination of Aldehydes
Published in	Journal of the American Chemical Society, February 2016
DOI	10.1021/jacs.5b10876
Pubmed ID	26772311
Authors	Melissa A. Ashley, Jennifer S. Hirschi, Joseph A. Izzo, Mathew J. Vetticatt
Abstract	The mechanism of L-proline catalyzed α-amination of 3-phenylpropionaldehyde was studied using a combination of experimental kinetic isotope effects (KIEs) and theoretical calculations. Observation of a significant carbonyl 13C KIE and a large primary (1°) α-deuterium KIE support rate-determining enamine formation. Theoretical predictions of KIEs exclude the widely accepted mechanism - enamine formation via intramolecular deprotonation of an iminium carboxylate intermediate (7). An E2-elimination mechanism catalyzed by a bifunctional base, that directly forms an N-protonated enamine species (12•H+) from an oxazolidinone (11) intermediate, accounts for the experimental KIEs. These findings provide the first experimental picture of the transition state geometry of enamine formation and clarify the role of oxazolidinones as non-parasitic intermediates in proline catalysis.

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Country	Count	As %
Unknown	2	100%

Demographic breakdown

Type	Count	As %
Members of the public	2	100%

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The data shown below were compiled from readership statistics for 49 Mendeley readers of this research output. Click here to see the associated Mendeley record.

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Country	Count	As %
Unknown	49	100%

Demographic breakdown

Readers by professional status	Count	As %
Researcher	2	4%
Student > Ph. D. Student	2	4%
Student > Master	1	2%
Unknown	44	90%

Readers by discipline	Count	As %
Chemistry	3	6%
Biochemistry, Genetics and Molecular Biology	1	2%
Environmental Science	1	2%
Unknown	44	90%

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This research output has an Altmetric Attention Score of 10. This is our high-level measure of the quality and quantity of online attention that it has received. This Attention Score, as well as the ranking and number of research outputs shown below, was calculated when the research output was last mentioned on 05 February 2016.

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#1,343,691

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#3,948

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#45,525

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Outputs of similar age from Journal of the American Chemical Society

#70

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Altmetric has tracked 12,368,126 research outputs across all sources so far. Compared to these this one has done well and is in the 89th percentile: it's in the top 25% of all research outputs ever tracked by Altmetric.

So far Altmetric has tracked 45,992 research outputs from this source. They typically receive a little more attention than average, with a mean Attention Score of 5.3. This one has done particularly well, scoring higher than 91% of its peers.

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We're also able to compare this research output to 436 others from the same source and published within six weeks on either side of this one. This one has done well, scoring higher than 83% of its contemporaries.

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Isotope Effects Reveal the Mechanism of Enamine Formation in l -Proline-Catalyzed α-Amination of Aldehydes

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