Search results for "reductive elimination"
showing 10 items of 23 documents
Etherification of Functionalized Phenols with Chloroheteroarenes at Low Palladium Loading: Theoretical Assessment of the Role of Triphosphane Ligands…
2011
The present study highlights the potential of robust tridentate ferrocenylphosphanes with controlled conformation as catalytic auxiliaries in CO bond formation reactions. Air-stable palladium triphosphane systems are efficient for selective heteroaryl ether synthesis by using as little as 0.2 mol% of catalyst. These findings represent an economically attractive and clean etherification of functionalized phenols, electron-rich, electron-poor and para-, meta- or ortho-substituted substrates, with heteroaryl chlorides, including pyridines, hydroxylated pyridine, pyrimidines and thiazole. The etherification tolerates very important functions in various positions, such as cyano, methoxy, amino, …
Diastereoselective Synthesis of Dialkylated Bis(phosphino)ferrocenes: Their Use in Promoting Silver-Mediated Nucleophilic Fluorination of Chloroquino…
2017
International audience; The diastereoselective synthesis of dialkylated ferrocenyl bis(phosphane)s bearing aryl, alkyl, and hetero- or polycyclic substituents on the phosphino groups is reported, together with their characterization in the solid state by X-ray structure analysis and in solution by multinuclear NMR spectroscopy. Introduction of various alkyl groups on the ferrocene backbone, namely, tert-butyl, isopropyl, and trimethylsilyl, has a significant influence on the stereoselectivity of the ensuing lithiation/phosphination reactions. Only the introduction of the tert-butyl groups ensures both a high yield and perfect diastereoselectivity, which leads to the exclusive formation of t…
On the mechanism of imine elimination from Fischer tungsten carbene complexes
2016
(Aminoferrocenyl)(ferrocenyl)carbene(pentacarbonyl)tungsten(0) (CO)5W=C(NHFc)Fc (W(CO)5(E-2)) is synthesized by nucleophilic substitution of the ethoxy group of (CO)5W=C(OEt)Fc (M(CO)5(1Et)) by ferrocenyl amide Fc-NH– (Fc = ferrocenyl). W(CO)5(E-2) thermally and photochemically eliminates bulky E-1,2-diferrocenylimine (E-3) via a formal 1,2-H shift from the N to the carbene C atom. Kinetic and mechanistic studies to the formation of imine E-3 are performed by NMR, IR and UV–vis spectroscopy and liquid injection field desorption ionization (LIFDI) mass spectrometry as well as by trapping experiments for low-coordinate tungsten complexes with triphenylphosphane. W(CO)5(E-2) decays thermally i…
Cyclometalated Au(III) Complexes for Cysteine Arylation in Zinc Finger Protein Domains: Towards Controlled Reductive Elimination
2019
With the aim of exploiting the use of organometallic species for the efficient modification of proteins through C-atom transfer, the gold-mediated cysteine arylation through a reductive elimination process occurring from the reaction of cyclometalated AuIII C^N complexes with a zinc finger peptide (Cys2His2 type) is here reported. Among the four selected AuIII cyclometalated compounds, the [Au(CCON)Cl2] complex featuring the 2-benzoylpyridine (CCON) scaffold was identified as the most prone to reductive elimination and Cys arylation in buffered aqueous solution (pH 7.4) at 37 °C by high-resolution LC electrospray ionization mass spectrometry. DFT and quantum mechanics/molecular mechanics (Q…
Exploring the Chemoselectivity towards Cysteine Arylation by Cyclometallated Au III Compounds: New Mechanistic Insights
2020
To gain more insight into the factors controlling the efficient cysteine arylation by cyclometalated Au(III) complexes, the reaction between selected gold compounds and different peptides was investigated by high‐resolution liquid chromatography electrospray ionization mass spectrometry (HR‐LC‐ESI‐MS). The deducted mechanisms of C–S cross‐coupling, also supported by density functional theory (DFT) and quantum mechanics/molecular mechanics (QM/MM) calculations, evidenced the key role of secondary peptidic gold binding sites in favouring the process of reductive elimination.
Carbon–Phosphorus Coupling from C^N Cyclometalated Au III Complexes
2020
Abstract With the aim of exploiting new organometallic species for cross‐coupling reactions, we report here on the AuIII‐mediated Caryl−P bond formation occurring upon reaction of C^N cyclometalated AuIII complexes with phosphines. The [Au(C^N)Cl2] complex 1 featuring the bidentate 2‐benzoylpyridine (CCON) scaffold was found to react with PTA (1,3,5‐triaza‐7‐phosphaadamantane) under mild conditions, including in water, to afford the corresponding phosphonium 5 through C−P reductive elimination. A mechanism is proposed for the title reaction based on in situ 31P{1H} NMR and HR‐ESI‐MS analyses combined with DFT calculations. The C−P coupling has been generalized to other C^N cyclometalated Au…
Generation, Characterization, and Electrochemical Behavior of the Palladium-Hydride Cluster [Pd3(dppm)3(3-CO)(3-H)]+ (dppm=Bis(diphenylphosphinometha…
2007
Addition of formate on the dicationic cluster [Pd(3)(dppm)(3)(mu(3)-CO)](2+) (dppm=bis(diphenylphosphinomethane) affords quantitatively the hydride cluster [Pd(3)(dppm)(3)(mu(3)-CO)(mu(3)-H)](+). This new palladium-hydride cluster has been characterised by (1)H NMR, (31)P NMR and UV/Vis spectroscopy and MALDI-TOF mass spectrometry. The unambiguous identification of the capping hydride was made from (2)H NMR spectroscopy by using DCO(2) (-) as starting material. The mechanism of the hydride complex formation was investigated by UV/Vis stopped-flow methods. The kinetic data are consistent with a two-step process involving: 1) host-guest interactions between HCO(2) (-) and [Pd(3)(dppm)(3)(mu(3…
Synthese von Giycopeptiden: Selektive C-terminale Deblockierung und Peptidkettenverlängerung an Glucosylserin-Derivaten
1983
Benzyloxycarbonyl-(Z-)serin-2-bromethylester (3b) wird mit 2,3,4,6-Tetra-O-benzoyl-α-D-gluco-pyranosylbromid (14) zum Glucosylserinester 15 verknupft. Nach Umwandlung in den entsprechenden 2-Iodethylester 23 wird die Carboxygruppe durch Eliminierung mit Zink selektiv deblockiert. Dabei bleiben die Z- und die Kohlenhydrat-Schutzgruppen sowie die empfindliche O-glycosidische Bindung unverandert erhalten. Das Glycosyl-Z-serin 24 reagiert mit Aminosaure-2-bromethylestern 2 zu geschutzten Glycodipeptid-2-bromethylestern 18, die nach selektiver Carboxydeblockierung zu Glycotripeptidestern 25 C-terminal verlangert werden. Wahrend geschutzte Serin-Dipeptide 5 mit 14 zu Konjugaten 18 glycosyliert we…
Studien zum Vorgang der Wasserstoffübertragung, 68. Die reduktive Überführung aromatischer Säurechloride in Diarylacetylene mit Lithiumamalgam in ein…
1983
Endioldiester A, die durch “Acylierende reduktive Dimerisierung” mit Lithiumamalgam (Li/Hg) nach (1) zuganglich sind, werden mit zwei weiteren Reduktionsaquivalenten nach (2) durch “Reduktive Eliminierung” in Acetylenderivate ubergefuhrt. Hierbei hat sich praparativ das Eintopfverfahren in der Zweistufenarbeitsweise bewahrt. Auch mit Natriumamalgam (Na/Hg) und Kaliumamalgam (K/Hg) gelingt die reduktive Eliminierung nach (2) sowohl von cis- als auch von trans-Endiol-diestern zu Acetylenverbindungen mit guten Ausbeuten. Voraussetzung fur den erfolgreichen Ablauf der Reaktion (2) ist die direkte Verknupfung von zwei Aromaten mit der C C-Doppelbindung in den Endiol-diestern. Endiol-diester mit …
Stereo and regioselectivity in the phenylation of cationic allylpalladium(II) α-diimine complexes by tetraphenylborate anion
1993
The reaction of the cationic complex [Pd(4-methoxy-1,3-η3-cyclohexenyl)(py-2-CHNC6H4OMe-4)]+ (1) with BPh4− in the presence of fumaronitrile yields trans-3-methoxy-6-phenylcyclohexene (2a) and trans-4-methoxy-3-phenylcyclohexene (2b), in ca. 1 : 1 molar ratio. The trans stereochemistry of these products implies that the phenylation of the allyl ligand involves prior transfer of a phenyl group from BPh4− to the metal, followed by reductive coupling of the organic moieties. In the reactions of [Pd(η3-1,1-R1,R2-C3H3)(NN′)]+ (3) [NN′ 4-MeOH4C6NCHCHNC6H4OMe-4; py-2-CHNR (R C6H4OMe-4, Me, or CMe3), 2,2′-bipyridine (bipy); R1 H, R2 Ph, Me; R1 R2 Me; with BPh4− in the presence of …