Binding of Diamines to <i>n</i>-Butyllithium Dimers:  Relative Solvation Energies and Evidence of Correlated Solvation

Hoffmann, Daniele; Collum, David B.

doi:10.1021/ja971512p

Cited by 72 publications

(29 citation statements)

References 14 publications

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“…34,35 The example in Figure 7c is characteristic of the occasional intervention of a mixed solvated dimer (eq 4). Strongly coordinating monodentate ligands can displace one chelated TMEDA ligand from the dimer.…”

Section: Resultsmentioning

confidence: 99%

Structure Determination Using the Method of Continuous Variation: Lithium Phenolates Solvated by Protic and Dipolar Aprotic Ligands

Tomasevich

Collum

2013

J. Org. Chem.

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The method of continuous variation (MCV) in conjunction with 6Li NMR spectroscopy was used to characterize four lithium phenolates solvated by a range of solvents including N,N,N′,N′-tetramethylethylenediamine, Et2O, pyridine, protic amines, alcohols, and highly dipolar aprotic solvents. Dimers, trimers, and tetramers were observed, depending on the precise lithium phenolate-solvent combinations. Competition experiments (solvent swaps) provide insights into relative solvation energies propensities toward mixed solvation.

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Section: Resultsmentioning

confidence: 99%

Structure Determination Using the Method of Continuous Variation: Lithium Phenolates Solvated by Protic and Dipolar Aprotic Ligands

Tomasevich

Collum

2013

J. Org. Chem.

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“…[18] Figure 4 shows the corresponding Eyring plots. Again, we obtained an increase in the proportion of the anti isomer relative to when pure hexane was used, especially with TMEDA.…”

Section: Resultsmentioning

confidence: 99%

Solvent and Temperature Effects on Diastereofacial Selectivity: Amines as Co‐Solvents in n‐Butyllithium Addition to α‐Chiral Aldehydes

et al. 2003

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Temperature-dependent selectivity in nucleophilic additions to α-chiral aldehydes is affected by solvent mixtures. In this context, we investigated the effect on diastereoselectivity of tertiary amines as co-solvents. Addition of 5 mol% of an amine to hexane strongly influences the anti/syn ratio in the additions of nBuLi to 2-phenylpropanal and to (2S)-2-[(tertbutyl)dimethylsilyloxy]-2-propanal. In these hexane/amine mixtures as reaction solvents, we observed diastereoselectivities higher than those obtained in hexane. In the corresponding Eyring plots of ln(anti/syn) against the reciprocal temperature, we observed inversion temperatures (T inv ),

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“…[23] A polymeric structure has also been found with dimethoxyethane, in which the bidentate ether links adjacent nBuLi tetramers. [22a] Tetrameric n-butyllithium is also contained in the THF adduct with the ether molecules apically coordinating the lithium atoms.…”

Section: Deaggregation Of Commonly Used Alkyllithium Compoundsmentioning

confidence: 99%

Structure Formation Principles and Reactivity of Organolithium Compounds

Gessner

Däschlein

Strohmann

2009

Chemistry A European J

241

111

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The structure-reactivity relationship is an important feature of organolithium compounds. The knowledge of the structure of reactive species is crucial for the elucidation of reaction mechanisms and the understanding of observed selectivities. This concept article gives an overview over the structural principles of lithium organics and their Lewis base coordinated complexes in the solid state. The transition from the oligomeric parent structures to smaller adducts, such as dimers and monomers, as well as special degrees of aggregation is presented. Besides the commonly used alkyllithium compounds, a short overview over the structural principles of the higher homologous silyllithium compounds is given. Moreover, the structure-reactivity relationship is depicted by means of the reactivity of the Lewis bases towards intramolecular decomposition reactions with the organolithium compound. Selected examples confirm the importance of structure elucidation for the understanding of mechanistic pathways and selectivities.

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Binding of Diamines to n-Butyllithium Dimers: Relative Solvation Energies and Evidence of Correlated Solvation

Cited by 72 publications

References 14 publications

Structure Determination Using the Method of Continuous Variation: Lithium Phenolates Solvated by Protic and Dipolar Aprotic Ligands

Structure Determination Using the Method of Continuous Variation: Lithium Phenolates Solvated by Protic and Dipolar Aprotic Ligands

Solvent and Temperature Effects on Diastereofacial Selectivity: Amines as Co‐Solvents in n‐Butyllithium Addition to α‐Chiral Aldehydes

Structure Formation Principles and Reactivity of Organolithium Compounds

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