Cyclopalladated Compounds as Resolving Agents for Racemic Mixtures of Ligands

Djukic, Jean‐Pierre

doi:10.1002/9783527623211.ch7

Cited by 8 publications

(4 citation statements)

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“…The latter generally binds the metal center quite stereospecifically anti to the donor ligand of the metallacycle. This elementary reaction was often used for the resolution of racemic chiral phosphanes from the related diastereomeric adducts obtained from enantiopure μ‐chlorido‐bridged palladacycles …”

Section: Introductionmentioning

confidence: 99%

“…This elementary reaction was often used for the resolution of racemic chiral phosphanes from the related diastereomeric adducts obtained from enantiopure m-chlorido-bridged palladacycles. [65] The reaction enthalpies in chlorobenzene (PhCl) solution were determined using ITC measurements. This dimer breaking reaction is known to work quite selectively.…”

Section: Introductionmentioning

confidence: 99%

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The Thermochemistry of London Dispersion‐Driven Transition Metal Reactions: Getting the ‘Right Answer for the Right Reason’

et al. 2014

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Reliable thermochemical measurements and theoretical predictions for reactions involving large transition metal complexes in which long-range intramolecular London dispersion interactions contribute significantly to their stabilization are still a challenge, particularly for reactions in solution. As an illustrative and chemically important example, two reactions are investigated where a large dipalladium complex is quenched by bulky phosphane ligands (triphenylphosphane and tricyclohexylphosphane). Reaction enthalpies and Gibbs free energies were measured by isotherm titration calorimetry (ITC) and theoretically ‘back-corrected’ to yield 0 K gas-phase reaction energies (ΔE). It is shown that the Gibbs free solvation energy calculated with continuum models represents the largest source of error in theoretical thermochemistry protocols. The (‘back-corrected’) experimental reaction energies were used to benchmark (dispersion-corrected) density functional and wave function theory methods. Particularly, we investigated whether the atom-pairwise D3 dispersion correction is also accurate for transition metal chemistry, and how accurately recently developed local coupled-cluster methods describe the important long-range electron correlation contributions. Both, modern dispersion-corrected density functions (e.g., PW6B95-D3(BJ) or B3LYP-NL), as well as the now possible DLPNO-CCSD(T) calculations, are within the ‘experimental’ gas phase reference value. The remaining uncertainties of 2–3 kcal mol−1 can be essentially attributed to the solvation models. Hence, the future for accurate theoretical thermochemistry of large transition metal reactions in solution is very promising.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

The Thermochemistry of London Dispersion‐Driven Transition Metal Reactions: Getting the ‘Right Answer for the Right Reason’

et al. 2014

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“…The metal-containing reagents are of a fundamentally different type from organic CDAs due to their ability to achieve coordinative bonding with the substrate. Among these coordinative chiral derivatizing agents (CCDAs), enantiopure cyclopalladated compounds (CPCs) occupy the leading position, most likely due to their wide application as resolving agents . Thus, the AC of numerous mono- and bidentate ligands has been assigned by means of X-ray crystallography and/or NMR techniques, using homochiral CN -palladacycles as a reference point.…”

Section: Introductionmentioning

confidence: 99%

Determination of the Absolute Configuration of CN-Palladacycles by ³¹P{¹H} NMR Spectroscopy Using (1R,2S,5R)-Menthyloxydiphenylphosphine as the Chiral Derivatizing Agent: Efficient Chirality Transfer in Phosphinite Adducts

et al. 2016

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A series of (1R)-MenOPPh2 phosphinite derivatives of α-arylalkylaminate CN-palladacycles of known absolute configuration was prepared. Their structure and stereochemistry were determined using different experimental (NMR spectroscopy and X-ray diffraction) and theoretical (density functional theory calculation) methods. Despite the conformational mobility of the phosphinite reagent and the highly remote position of its stereocenters from those of the cyclopalladated amine, efficient chirality transfer in the phosphinite cyclopalladated complexes was established. On the basis of these results, a new method for the determination of the absolute configuration of chiral CN-palladacycles was elaborated using the (1R)-MenOPPh2 phosphinite as a highly sensitive referee ligand and in situ 31P{1H} NMR spectroscopy as a control method. The proposed approach is a remarkable addition to the classical NMR techniques, increasing their versatility and excluding the isolation of the phosphinite derivatives.

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“… 1 In addition, they are also broadly applied in transition metal catalysis and organocatalysis as chiral ligands and chiral catalysts. 2 Compared with conventional methods using a stoichiometric amount of chiral starting materials or chiral reagents, 3 asymmetric catalytic approaches have attracted increasing attention in the construction of chiral phosphines. Among them, catalytic asymmetric hydrophosphination is one of the most direct and atom-economical ways for preparation of optically active phosphines.…”

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Enantioselective copper-catalyzed hydrophosphination of alkenyl isoquinolines

2023

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Cyclopalladated Compounds as Resolving Agents for Racemic Mixtures of Ligands

Cited by 8 publications

References 75 publications

The Thermochemistry of London Dispersion‐Driven Transition Metal Reactions: Getting the ‘Right Answer for the Right Reason’

The Thermochemistry of London Dispersion‐Driven Transition Metal Reactions: Getting the ‘Right Answer for the Right Reason’

Determination of the Absolute Configuration of CN-Palladacycles by ³¹P{¹H} NMR Spectroscopy Using (1R,2S,5R)-Menthyloxydiphenylphosphine as the Chiral Derivatizing Agent: Efficient Chirality Transfer in Phosphinite Adducts

Enantioselective copper-catalyzed hydrophosphination of alkenyl isoquinolines

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Cyclopalladated Compounds as Resolving Agents for Racemic Mixtures of Ligands

Cited by 8 publications

References 75 publications

The Thermochemistry of London Dispersion‐Driven Transition Metal Reactions: Getting the ‘Right Answer for the Right Reason’

The Thermochemistry of London Dispersion‐Driven Transition Metal Reactions: Getting the ‘Right Answer for the Right Reason’

Determination of the Absolute Configuration of CN-Palladacycles by 31P{1H} NMR Spectroscopy Using (1R,2S,5R)-Menthyloxydiphenylphosphine as the Chiral Derivatizing Agent: Efficient Chirality Transfer in Phosphinite Adducts

Enantioselective copper-catalyzed hydrophosphination of alkenyl isoquinolines

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Determination of the Absolute Configuration of CN-Palladacycles by ³¹P{¹H} NMR Spectroscopy Using (1R,2S,5R)-Menthyloxydiphenylphosphine as the Chiral Derivatizing Agent: Efficient Chirality Transfer in Phosphinite Adducts