Asymmetric synthesis of a rigid diphosphine ligand containing two phosphorus and four carbon stereogenic centres by means of a chiral palladium complex promoted Diels–Alder reaction

Leung, Pak‐Hing; Selvaratnam, S.; Cheng, Chih-Yuan; Mok, K. F.; Rees, Nicholas H.; McFarlane, William

doi:10.1039/a700314e

Cited by 32 publications

(20 citation statements)

References 10 publications

(2 reference statements)

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“…Despite the critical importance of chiral cyclopalladated dimers in catalysis, materials chemistry, optical resolution, the determination of enantiomeric excess and absolute configuration of chiral compounds, and studies on antitumor activity, as well as the promotion of asymmetric Diels−Alder reactions, 1a,d,e enantiopure cyclopalladated derivatives of ferrocene are scarce. − …”

Section: Introductionmentioning

confidence: 99%

Cyclic Ether Induced Asymmetric Cyclopalladation: Synthesis and Structural Characterization of Enantiopure Bis(μ-acetato)-Bridged Dimers of Planar Chiral Cyclopalladated Ferrocenylimines and Their Derivatives

1999

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Enantiopure bis(μ-acetato)-bridged planar chiral cyclopalladated products (R = H, Me) have been obtained by asymmetric cyclopalladation of the corresponding chiral ferrocenylimines with palladium(II) acetate and sodium acetate in methanol at room temperature with a high level of diastereoselectivity (product ratio syn-(+)-(R p,R,R,R p):syn-(−)-(S p,R,R,S p) ≈ syn-(−)-(S p,S,S,S p):syn-(+)-(R p,S,S,R p) ≈ 9:1). One or both acetato groups can be readily substituted by other anionic ligands to yield novel mixed-bridge or bis(μ-anion)-bridged planar chiral dimers of ferrocene derivatives. The first cis-type syn-(R p,S p) cyclopalladated dimer of ferrocenylimine has been obtained. The diphenylacetylene insertion reaction of a variety of anion-bridged planar chiral dimeric cyclopalladated derivatives of ferrocene has also been investigated. The absolute configurations of bis(μ-acetato)-, bis(μ-halogeno)-, (μ-1κS:2κN)-(μ-1κN:2κS)-thiocyanato-, and (μ-1κO:2κN)-(μ-1κN:2κO)-nitrito-bridged planar chiral dimers and bis(diphenylacetylene) insertion products have been elucidated by single-crystal X-ray analysis.

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Section: Introductionmentioning

confidence: 99%

Cyclic Ether Induced Asymmetric Cyclopalladation: Synthesis and Structural Characterization of Enantiopure Bis(μ-acetato)-Bridged Dimers of Planar Chiral Cyclopalladated Ferrocenylimines and Their Derivatives

1999

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“…53). This selectivity implies that six stereogenic centers are controlled during the cycloaddition [126,127].…”

Section: Reactivity In Cycloaddition Reactionsmentioning

confidence: 96%

Alkenylphosphines: Applications in Synthesis, Catalysis and Coordination Chemistry

Julienne¹,

Toulgoat²,

Delacroix

et al. 2010

COC

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Alkenylphosphines are compounds of great interest in view of their structures. The most interesting feature is the carboncarbon double bond, which is directly linked to the phosphorus atom. Nucleophilic addition or cycloaddition reactions can take place at this unsaturation, which can also be used as a coordinating part in the presence of a metal. Thus, alkenylphosphines have found numerous applications in various fields of chemistry. They are useful intermediates in organic synthesis: numerous studies are devoted to their transformation into bidentate ligands, to their use as precursors for dendrimer and polymer chemistry or as ligand for homogeneous catalysis. Due to the presence of both the phosphorus atom and the carbon-carbon double bond, they are also of great interest in coordination chemistry and their different bonding modes have been largely documented. Moreover, after complexation to transition metal, a great amount of work has been carried out on their reactivity in cycloaddition reactions, as well as in functionalization of the carbon-carbon double bond and other miscellaneous reactions. These main applications will be reviewed hereafter.

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“…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. To the best of our knowledge, there is only one report combining the experimental methods of the AC assignment with DFT calculations for a palladacycle-coordinated monodentate P*-chiral ligand…”

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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Asymmetric synthesis of a rigid diphosphine ligand containing two phosphorus and four carbon stereogenic centres by means of a chiral palladium complex promoted Diels–Alder reaction

Cited by 32 publications

References 10 publications

Cyclic Ether Induced Asymmetric Cyclopalladation: Synthesis and Structural Characterization of Enantiopure Bis(μ-acetato)-Bridged Dimers of Planar Chiral Cyclopalladated Ferrocenylimines and Their Derivatives

Cyclic Ether Induced Asymmetric Cyclopalladation: Synthesis and Structural Characterization of Enantiopure Bis(μ-acetato)-Bridged Dimers of Planar Chiral Cyclopalladated Ferrocenylimines and Their Derivatives

Alkenylphosphines: Applications in Synthesis, Catalysis and Coordination Chemistry

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

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Asymmetric synthesis of a rigid diphosphine ligand containing two phosphorus and four carbon stereogenic centres by means of a chiral palladium complex promoted Diels–Alder reaction

Cited by 32 publications

References 10 publications

Cyclic Ether Induced Asymmetric Cyclopalladation: Synthesis and Structural Characterization of Enantiopure Bis(μ-acetato)-Bridged Dimers of Planar Chiral Cyclopalladated Ferrocenylimines and Their Derivatives

Cyclic Ether Induced Asymmetric Cyclopalladation: Synthesis and Structural Characterization of Enantiopure Bis(μ-acetato)-Bridged Dimers of Planar Chiral Cyclopalladated Ferrocenylimines and Their Derivatives

Alkenylphosphines: Applications in Synthesis, Catalysis and Coordination Chemistry

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

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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