Author: Christine Salomon

The first unpaired electron placed inside a C3-symmetry P-chirogenic cluster

2010

The Pd(3)(dppm*)(3)(CO)(n+) enantiomers (n = 2 (2), 1 (3)) were prepared either from (R,R)- or (S,S)-P-chirogenic bis(phenyl-m-xylylphosphino)methane (dppm*; 1) and Pd(OAc)(2) in the presence of CF(3)CO(2)H, CO and water (n = 2), and then by reductive electrolysis (n = 1). The stable enantiomeric [Pd(3)((S,S)-dppm*)(3)(CO)](+)˙ (3), is the first C(3)-symmetry radical-cation M-M bonded cluster, therefore the odd electron is delocalized onto the Pd(3) frame within this symmetry. The novel chiral species have been characterized by circular dichroism (CD) of both enantiomers of the Pd(3)(dppm*)(3)(CO)(2+) clusters (2) and by EPR spectroscopy for the Pd(3)((S,S)-dppm*)(3)(CO)(+)˙ paramagnetic co…

Models MolecularSteric effectsStereochemistryChemistryElectron Spin Resonance SpectroscopyMolecular ConformationElectronsStereoisomerismlaw.inventionInorganic ChemistryMagneticsCrystallographyDelocalized electronParamagnetismUnpaired electronlawIntramolecular forceElectrochemistryOrganometallic CompoundsMolecular orbitalElectron paramagnetic resonanceHyperfine structurePalladiumDalton Transactions

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Enantiodivergent synthesis of P-chirogenic phosphines

2010

International audience; Several approaches for the enantiodivergent synthesis of P-chirogenic mono- and diphosphines are described, using ephedrine methodology and phosphine borane chemistry. Firstly, both enantiomers of a tertiary phosphine can be obtained starting from the same oxazaphospholidine borane complex, prepared from (+)-ephedrine, when changing the order of addition of the organolithium reagents during the synthetic pathway. The second approach is based on the chlorophosphine boranes, which react with an organolithium reagent, to afford the corresponding phosphines with inversion of configuration. In the case where the chlorophosphine borane reacts with the t-butyl lithium reage…

chemistry.chemical_classification010405 organic chemistryGeneral Chemical EngineeringArylBorane complexesEnantioselective synthesisBoranesAsymmetric synthesisGeneral Chemistry[CHIM.CATA]Chemical Sciences/CatalysisBorane010402 general chemistryOrganolithium reagent01 natural sciencesMedicinal chemistry0104 chemical scienceschemistry.chemical_compound[ CHIM.CATA ] Chemical Sciences/CatalysischemistryEnantiomersDiphosphinesOrganic chemistryChiral phosphinesPhosphineAlkyl

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The First P ‐Stereogenic 1D Coordination Polymers with the Metal Centers in the Backbone

2011

The enantiomeric ligands (R,R)- and (S,S)-bis(o-anisylphenylphosphanyl)methane (R,R-22 and S,S-22) and (R,R)- and (S,S)-bis(phenyl-m-xylylphosphanyl)methane (R,R-23 and S,S-23; dppm*), were treated with [Cu(NCCH3)4](BF4) and AgBF4 to produce the binuclear complexes [Cu2(dppm*)2(NCCH3)4](BF4)2 or [Ag2(dppm*)2](BF4)2, respectively. Then, these complexes were used as building blocks to prepare the first P-chirogenic 1D coordination polymers {[M2(dppm*)2(dmb)2](BF4)2}n [dppm* = (R,R)-22, (S,S)-22, (R,R)-23, (S,S)-23, M = Cu, Ag, dmb = 1,8-diisocyano-p-menthane] where M is part of the backbone of the polymer chain. The isostructural nature of these new polymers with the achiral parent polymers, …

Inorganic ChemistryMetalCircular dichroismCrystallographyChemistryvisual_artProton NMRvisual_art.visual_art_mediumEnantiomerIsostructuralChirality (chemistry)Bimetallic stripStereocenterEuropean Journal of Inorganic Chemistry

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Design of P-Chirogenic Aminophosphine-Phosphinite Ligands at Both Phosphorus Centers: Origin of Enantioselectivities in Pd-Catalyzed Allylic Reaction…

2020

International audience; We have recently patented an unprecedented stereospecific N→O phosphinyl migration process which transforms P-chirogenic aminophosphines into phosphinites. A fine design of aminophosphine phosphinite ligands (AMPP*) derived from ephedrine and bearing a P-chirogenic center either at the aminophosphine or phosphinite moiety, was performed. The synthesis of AMPP* ligands with P-chirogenic aminophosphine moiety was based on the well-established stereospecific reaction of oxazaphospholidine-borane with organolithium reagents, followed by trapping with a chlorophosphine and borane decomplexation. Concurrently, the preparation of AMPP* ligands with P-chirogenic phosphinite …

Allylic rearrangementPhosphinite010405 organic chemistry[CHIM.ORGA]Chemical Sciences/Organic chemistryOrganic ChemistryDABCOBorane010402 general chemistry01 natural sciencesMedicinal chemistry0104 chemical scienceschemistry.chemical_compoundStereospecificityNucleophilechemistryMoiety[CHIM]Chemical SciencesConformational isomerismThe Journal of organic chemistry

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