Search results for "Aminophosphines"
showing 3 items of 3 documents
Resolution of β-aminophosphines with chiral cyclopalladated complexes
2005
Abstract Resolution of the racemic chiral β-aminophosphines Ph 2 PCH 2 CH(Ph)NH(Ar) ( L 1 for Ar = C 6 H 5 and L 2 for Ar = 2,6-C 6 H 3 i Pr 2 ) has been investigated by use of different cyclopalladated complexes as chiral agents. The resulting complexes afford diastereomeric adducts in a 1:1 ratio. After successive crystallizations from ethanol, a d.e. of 98% was achieved for one aminophosphine palladium complex, while no significant d.e. was obtained after crystallizations from chlorinated solvents. The X-ray structure analysis has pointed out intermolecular hydrogen interactions N–H⋯Cl between the P,N ligand and the chloride ion, which are responsible for the formation and stabilization …
New chiral α-aminophosphine oxides and sulfides: an unprecedented rhodium-catalyzed ligand epimerization
2001
International audience; New chiral α-aminophosphine oxide N,P(O) and sulfide N,P(S) ligands have been prepared in one-pot syntheses by addition of Ph2PH to (S)-PhCH[double bond, length half m-dash]NCH(Ph)CH3, followed by oxidation with O2 or S8. Crystallization from cold methanol leads to the isolation of an enantiomerically pure single N,P(O) diastereomer and to a 1 : 1 mixture of the two N,P(S) diastereomers. The coordination chemistry of these ligands with [RhCl(COD)]2 and [RhCl(CO)2]2 has been investigated under argon and syngas. At high temperatures, a P–C oxidative addition of the N,P(O) ligand followed by imine elimination leads to several hydrido rhodium species. The complexes conta…
Input of P, N-(phosphanyl, amino)-ferrocene hybrid derivatives in late transition metals catalysis
2018
International audience; Unequally functionalized ferrocenes give access to valuable hemilabile reactivity in catalytic reaction. We address the synthesis of hybrid (P, N)-ferrocenyl compounds for which recent catalytic breakthrough applications have been reported, transversely in late transition metals chemistry. Palladium, nickel, rhodium, iridium, and emerging iron and gold catalysis are illustrated from selected examples, which include CC bond formation from cross-coupling and polymerization, allylic substitution, cyanation, hydroformylation, CH arylation and silylation and hydrogenation reactions.