Are sp lithiated carbons more nucleophilic than sp2 or sp3 ones? A comparative DFT study of the condensation of propynyllithium aggregates on formaldehyde.

International audienceThe interaction between 1-propynyllithium, taken as a model of sp organolithium compound, and formaldehyde has been investigated with DFT theoretical methods. The unsolvated monomer, homogeneous dimer, trimer, tetramer, and hexamer have been considered, as well as the mixed aggregates with lithium dimethylamide in various oligomeric forms. In most cases, the separate entities, their docking complexes, the transition states, and the condensation products have been characterized. Overall, the general reaction scheme remains the same whatever the hybridization and the aggregation. However, the dimeric sp nucleophiles are expected to be more reactive (at least in kinetic conditions), while monomeric sp(3) entities would be the best nucleophiles in kinetic and thermodynamic conditions, even if its docking is the least exothermic. This work also suggests that the aggregation plays a relatively limited role on the model reaction

A DFT Theoretical Study of the Condensation of Aggregates of sp 2 Organolithium Compounds on Formaldehyde

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Theoretical quantification of the electrostatic contribution to complexes involving organolithium compounds

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

International audienceThe 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

A DFT Theoretical Analysis of Aldehyde Condensation Pathways onto Methyllithium, Lithium Dimethylamide, and Their Aggregates

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The phases and dynamics of succinonitrile: An NMR absorption line study

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Lithium Amide Protected against Hydrolysis by Aggregated Lithium Halides: An MS + DFT Investigation

International audienceSupported by mass spectrometry experiments, DFT computations indicate that the lithium amide of a 3-aminopyrrolidine (lithium benzhydryl(1-benzylpyrrolidin-3-yl)amide, 1-Li) is protected, up to a certain limit, against hydrolysis when it is aggregated with a strongly polar partner such as LiCl, LiBr, or MeLi

Why Are Monomeric Lithium Amides Planar?

International audienc

Influence of the Correlation, Aggregation, and Solvation on ab initio Computed Li−C, Li−N, and Li−Li NMR Coupling Constants

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Theoretical Investigations of the Influence of Pressure on the Selectivity of the Michael Addition of Diphenylmethaneamine to Stereogenic Crotonates

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