Base or nucleophile? DFT finally elucidates the origin of the selectivity between the competitive reactions triggered by MeLi or LDA on propanal

The competition between basicity and nucleophilicity of two standard organolithium reagents was studied using DFT. Comparing the reactivity of solvated (MeLi)2 and (LDA)2 toward propanal finally explains why methyllithium adds onto the carbonyl while LDA deprotonates the α-position, in accord with e...

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Bibliographic Details
Published in:Chemical communications (Cambridge, England) England), 2015-06, Vol.51 (48), p.9801-9804
Main Authors: Marchois, J, Fressigné, C, Lecachey, B, Maddaluno, J
Format: Article
Language:English
Subjects:
Basicity
Carbonyls
Chemical Sciences
Competition
Nucleophiles
Organic chemistry
Origins
Selectivity
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Summary:The competition between basicity and nucleophilicity of two standard organolithium reagents was studied using DFT. Comparing the reactivity of solvated (MeLi)2 and (LDA)2 toward propanal finally explains why methyllithium adds onto the carbonyl while LDA deprotonates the α-position, in accord with experiment and Ireland's deprotonation TS.
ISSN:1359-7345
1364-548X
DOI:10.1039/c5cc01549a