0000000000013077
AUTHOR
Aziz Fihri
Use of a bulky phosphine of weak σ-donicity with palladium as a versatile and highly-active catalytic system: allylation and arylation coupling reactions at 10−1–10−4mol% catalyst loadings of ferrocenyl bis(difurylphosphine)/Pd
Abstract Carbon–carbon(sp2–sp2 and sp1–sp2) and carbon–nitrogen (nucleophilic allylation) coupling processes are promoted by a catalytic system containing [PdCl(η3–C3H5)]2 with the new ferrocenyl bis(difurylphosphine) 1,1′-bis[di(5-methyl-2-furyl)phosphino]ferrocene, Fc[P(FuMe)2]2. Starting from aryl bromides or allylic acetates this versatile catalyst system may be used at low palladium loadings (10−1–10−4 mol%) in some Heck, Suzuki, Sonogashira and allylic amination reactions to give cross-coupled products in excellent yield. Remarkably high activity is obtained in allylic substitution reactions, providing a significant impetus for the development of bulky phosphines possessing weak σ-don…
Enlarging the family of ferrocenylphosphine dinuclear rhodium complexes: synthesis and X-ray structure of a novel “A-frame”-type trimetallic Rh/Fe/Rh complex
Abstract The symmetrically substituted ligand 1,1 ′ -bis[di(5-methyl-2-furyl)phosphino]ferrocene ( 1 ) has been obtained from the bromophosphine BrP(Fu Me ) 2 and the dilithioferrocene/TMEDA adduct. The quantitative addition of this ferrocene derivative to the tetracarbonyl dimer [(CO) 4 Rh 2 {μ-(S t Bu) 2 }] leads, through decarbonylation, to the dinuclear rhodium complex [(CO) 2 Rh 2 {μ-(S t Bu) 2 }{μ- P , P -Fc[P(Fu Me ) 2 ] 2 }] ( 2 ) in high yield. A X-ray structure [ orthorhombic , space group P 2 1 2 1 2 1 ; a =11.2982(2) A, b =13.3165(3) A, c =27.2687(7) A] and the solution multinuclear NMR characterization are reported, which show that the rare “quasi-closed bridging” A-frame struc…
"Through-space" nuclear spin-spin J(PP) coupling in tetraphosphine ferrocenyl derivatives: a (31)P NMR and X-ray structure correlation study for coordination complexes.
Herein, we report on (31)P(31)P solution-phase "through-space" nuclear spin-spin coupling constants (J(PP)) from a novel family of organometallic tetraphosphine nickel and palladium complexes. These J(PP) constants were accurately determined through NMR iterative simulation based on the second-order spectra obtained for the compounds. The corresponding solid-state X-ray structures of the complexes were determined, and the "through-space" P.P distances are reported. Due to the blocked conformation of the species in solution, a qualitative and semiquantitative experimental correlation is obtained, which links the geometric parameters and the intensity of the corresponding P.P coupling constan…
Efficient palladium–ferrocenylphosphine catalytic systems for allylic amination of monoterpene derivatives
Ferrocenylphosphines added to [Pd(µ-Cl)(η3-C3H5)]2 dimeric precursor produce efficient catalysts to effect the allylic amination of terpenic allylacetates. Particularly convenient are tetrakis(diphenylphosphino)ferrocene and 1,1′-bis(diphenylphosphino)ferrocene, which allow the amination of allylacetates with good to excellent selectivity, and have turnover numbers as high as 80 000, for instance, for the formation of allylaniline. Herein, we report on reactions that selectively transform geranylacetate, nerylacetate, linalylacetate and perillylacetate into the corresponding allylic amines. These preparative methods give facile access to various products of great potential industrial intere…
Catalytic Efficiency of a New Tridentate Ferrocenyl Phosphine Auxiliary: Sonogashira Cross-Coupling Reactions of Alkynes with Aryl Bromides and Chlorides at Low Catalyst Loadings of 10-1 to 10-4 mol %.
[structure: see text] The catalytic activity in Sonogashira cross-coupling reactions of alkynes with a variety of aryl halides (including chlorides) using a multidentate ferrocenyl phosphine is presented. The novel mixed ferrocenyl aryl/alkyl triphosphine is thermally stable and insensitive to air or moisture, and its robustness allows aryl alkynylation at 10(-1) to 10(-4) mol % catalyst loadings with TONs up to 250,000. Copper-free coupling using phenylacetylene is also accessible in good yield.
Performances of symmetrical achiral ferrocenylphosphine ligands in palladium-catalyzed cross-coupling reactions: A review of syntheses, catalytic applications and structural properties
Abstract Ferrocene derivatives bearing donor atoms led to the generation of several classes of metallo-ligands, which collectively show an impressive diversity of applications, especially in metal-catalyzed modern organic reactions. Based on the impetus provided by the use of the diphosphine 1,1′-bis(diphenylphosphino)ferrocene (dppf) the investigations directed towards the synthesis of new ferrocenylphosphines remain of fundamental and industrial interest. The present review aims to describe the performances in palladium-catalyzed cross-coupling reactions of symmetrical achiral ferrocenylphosphine ligands, mainly diphosphines. We specifically choose to restrict our review efforts to these …
Diphosphines of dppf-Type Incorporating Electron-Withdrawing Furyl Moieties Substantially Improve the Palladium-Catalysed Amination of Allyl Acetates
Highly active Pd/diphosphine catalytic systems incorporating new, air-stable ferrocenyl-furylphosphines allow nucleophilic allylic amination at room temperature with unprecedented turnover frequencies. For instance, in the presence of 0.01 mol % catalyst the coupling of aniline to allyl acetate occurs at a TOF of more than 10,000 h - 1 ; even the addition of the less nucleophile morpholine to allyl acetate is observed with a TOF of 4250 h - 1 . The amination of the sterically demanding geranyl acetate, a monoterpene derivative of interest in the flavour industry, at low catalyst loadings demonstrates the scope of this methodology, which provides in addition noticeable advantages in terms of…
{1,1′-Bis[bis(5-methyl-2-furyl)phosphino]ferrocene-κ2P,P′}dichloroplatinum(II) dichloromethane hemisolvate
The synthesis of the title compound, [FePtCl2(C15H14O2P)2]·0.5CH2Cl2, has been achieved by reacting PtCl2(PhCN)2 with the 1,1′-bis[bis(5-methyl-2-furyl)phosphino]ferrocene chelating ligand. The environment at the Pt atom can be described as distorted square-planar, with two cis-Cl atoms and two cis-P atoms.
Vers une catalyse durable, économe d'atomes et éco-responsable : 0,0001 % de métal, une dose presque homéopathique pour la synthèse pharmaceutique et agrochimique
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