The Structure of "R2Cu(CN)Li2" Lithium Cuprates: Lower-Order Aggregates of Gilman Reagents and Organo Lithium Compounds

Snyder, James P.; Spangler, Dale; Behling, James R.; Rossiter, Bryant E.

doi:10.1021/jo00089a001

Cited by 67 publications

(38 citation statements)

References 3 publications

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“…This led to the conclusion that higher-order structures were less stable than their lowerorder analogues. 20 Whilst in response to these finding it was Floris Chevallier is an Associate Professor at the University of Rennes 1 (Rennes, France). He studied (organic) chemistry at the universities of Orléans and Nantes.…”

Section: Lipshutz Cuprates: the Solid-state Evidencementioning

confidence: 99%

New avenues in the directed deprotometallation of aromatics: recent advances in directed cupration

et al. 2014

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Recent advances in the selective deprotometallation of aromatic reagents using alkali metal cuprates are reported. The ability of these synergic bases to effect deprotonation under the influence of a directing group is explored in the context of achieving new and more efficient organic transformations whilst encouraging greater ancillary group tolerance by the base. Developments in our understanding of the structural chemistry of alkali metal cuprates are reported, with both Gilman cuprates of the type R2CuLi and Lipshutz and related cuprates of the type R2Cu(X)Li2 (X = inorganic anion) elucidated and rationalised in terms of ligand sterics. The generation of new types of cuprate motif are introduced through the development of adducts between different classes of cuprate. The use of DFT methods to interrogate the mechanistic pathways towards deprotonative metallation is described. Theoretical modelling of in situ rearrangements undergone by the cuprate base are discussed, with a view to understanding the relationship between R2CuLi and R2Cu(X)Li2, their interconversion and the implications of this for cuprate reactivity. The advent of a new class of adduct between different cuprate types is developed and interpreted in terms of the options for expelling LiX from R2Cu(X)Li2. Applications in the field of medicinal chemistry and (hetero)arene derivatization are explored.

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Section: Lipshutz Cuprates: the Solid-state Evidencementioning

confidence: 99%

New avenues in the directed deprotometallation of aromatics: recent advances in directed cupration

et al. 2014

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“…With the aid of 13 C, 6 Li, and 15 N NMR data [153], Bertz was able to point out that cyanide was not attached to copper(I) in the Lipshutz mix, and started the controversy [154,155]. Physical measurements by Penner-Hahn [156] and Lipshutz [157], and theoretical studies by Snyder [158], Penner-Hahn, and Frenking [159] contributed much to the discussion. All the crystallographic data for cyanocuprates of ''higher-order stoichiometry'' recently reported by Boche [160] and van Koten [161] indicated that the cyanide anion is coordinated to lithium and not to copper.…”

Section: ð10:15þmentioning

confidence: 99%

Mechanisms of Copper‐mediated Addition and Substitution Reactions

Mori¹,

Nakamura²

2002

Modern Organocopper Chemistry

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“…[50] NMR investigations also established that cuprates are dimers in DMS, [10] and X-ray crystal structures of unhindered cuprates prepared in ether [51,52] or DMS [53,54] reveal a dimer motif. The solution structure of the 2:1 cyanocuprate R 2 CuLiĹ iCN has been proposed to be one of several possible heterodimers of R 2 CuLi and LiCN, [14c, 15] and 15 N NMR is consistent with C.…”

Section: Reactions With Cyimentioning

confidence: 99%

Re-evaluation of Organocuprate Reactivity: Logarithmic Reactivity Profiles for Iodo- versus Cyano-Gilman Reagents in the Reactions of Organocuprates with 2-Cyclohexenone and Iodocyclohexane

Bertz¹,

Chopra

Eriksson

et al. 1999

Chem. Eur. J.

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Iodo-Gilman reagents Me 2 -CuLi´LiI, Bu 2 CuLi´LiI, and BuThCuLi´LiI and cyano-Gilman reagents (ne Â e ªhigher order cyanocupratesº Me 2 CuLi´LiCN, Bu 2 CuLi´LiCN, and BuThCuLi´LiCN react with 2-cyclohexenone at various rates, which depend upon the R groups (Me, Bu, Th thienyl), Li salt (LiI vs. LiCN), solvent (ether vs. THF), and amount of trimethylsilyl chloride (TMSCl) additive. The effect of the Li salt (CuI vs. CuCN precursor) is less than that of solvent or TMSCl. The butylcuprate-iodocyclohexane reaction has also been examined as a function of Li salt, solvent, and TMSCl additive, and similar effects are observed. The reactivity matrix R with elements r i,j is a convenient way to store and present a large amount of relative reactivity data. Entry r i,j is the ratio of the rate with reagent i to the rate with reagent j, which we approximate by using yields measured after a short time (4 s). The logarithmic reactivity profile (LRP) provides an efficient means for determining yields under conditions where such comparisons are valid. The results of a large number of 4-point LRPs and related reactions are tabulated and analyzed to provide a clearer picture of organocuprate reactivity.

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The Structure of "R2Cu(CN)Li2" Lithium Cuprates: Lower-Order Aggregates of Gilman Reagents and Organo Lithium Compounds

Cited by 67 publications

References 3 publications

New avenues in the directed deprotometallation of aromatics: recent advances in directed cupration

New avenues in the directed deprotometallation of aromatics: recent advances in directed cupration

Mechanisms of Copper‐mediated Addition and Substitution Reactions

Re-evaluation of Organocuprate Reactivity: Logarithmic Reactivity Profiles for Iodo- versus Cyano-Gilman Reagents in the Reactions of Organocuprates with 2-Cyclohexenone and Iodocyclohexane

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