49763-41-9

Usage

Uses

Used in Chemical Synthesis:
Chloro(tricyclohexylphosphine)gold(I) is used as a catalyst for a variety of chemical reactions, facilitating the formation of new chemical bonds and improving the efficiency of the processes.
Used in Formal Tandem Bicyclizations:
In the field of organic chemistry, Chloro(tricyclohexylphosphine)gold(I) is used as a catalyst for formal tandem bicyclizations of styrylindoles with alkynyl alkenones. This application allows for the formation of complex molecular structures with potential applications in pharmaceuticals and materials science.
Used in Addition of X-H Bonds to Carbon-Carbon Multiple Bonds:
Chloro(tricyclohexylphosphine)gold(I) is employed as a catalyst in the addition of X-H bonds (where X can be a variety of atoms or groups) to carbon-carbon multiple bonds, such as alkenes and alkynes. This reaction type is crucial for the synthesis of various organic compounds and materials.
Used in Arylation of Pyrazine or Pyridine:
In the pharmaceutical industry, Chloro(tricyclohexylphosphine)gold(I) is used as a catalyst for the arylation of pyrazine or pyridine with aryl bromides. This reaction is essential for the synthesis of various heterocyclic compounds with potential applications as pharmaceuticals and agrochemicals.
Used in Hydroarylation of Alkenes with Indoles:
Chloro(tricyclohexylphosphine)gold(I) is utilized as a catalyst in the hydroarylation of alkenes with indoles, a reaction that is important for the synthesis of indole-containing compounds, which are often found in natural products and pharmaceuticals.
Used in Cyclization:
In the field of organic synthesis, Chloro(tricyclohexylphosphine)gold(I) is used as a catalyst for cyclization reactions, which involve the formation of a ring structure in a molecule. This type of reaction is essential for the synthesis of various cyclic compounds with potential applications in pharmaceuticals, agrochemicals, and materials science.
Used in Hydroamination:
Chloro(tricyclohexylphosphine)gold(I) is employed as a catalyst in hydroamination reactions, which involve the addition of an amine group to a carbon-carbon multiple bond. This reaction is important for the synthesis of various amine-containing compounds, which are often found in pharmaceuticals, agrochemicals, and other specialty chemicals.

Upstream product

• 98938-44-4 5.6-μ-(AuPCy3)-nido-B10H13 
• 2622-14-2 tricyclohexylphosphine 
• 7647-01-0 hydrogenchloride 
• 7440-57-5 gold 
• 29892-37-3 chloro(dimethylsulfide) gold(I) 
• 932-72-9 (Dichloroiodo)benzene 
• 64-17-5 ethanol 
• 39929-21-0 (tetrahydrothiophene)gold(I) chloride 
• 1190715-83-3 [AuCl₃(P(C₆H₁₁)3)] 

Downstream Products

• 98938-44-4 5.6-μ-(AuPCy3)-nido-B10H13 
• 111852-76-7 (H₃C)C₃H₂N₂SAuP(C₆H₁₁)3 
• 113488-95-2 {Fe(CO)4(Au(P(C₆H₁₁)3))2} 
• 122566-83-0 {Fe₄(CO)12Au₂((P(C₆H₁₁)3)2)BH}*CH₂Cl₂ 
• 115403-04-8 C₂₃H₃₆AuN₄PS 
• 149160-56-5 {(Cy)3phosphinegold(I)-SC(=NPh)O-ethyl} 
• 147998-61-6 {Au(P(C₆H₁₁)3)(SC₄H₃N₂)} 
• 141292-26-4 HFe₄(CO)12BHAu(P(C₆H₁₁)3) 
• 143933-87-3 (1,1,1,3,3,3-hexafluoro-2-propoxo)(tricyclohexylphosphine)gold(I) 
• 106529-83-3 1,3-(tri-cyclo-hexylphosphinegold(I))2-5,5-diethyl-barbituric acid 
• 72752-35-3 [Au(P(C₆H₁₁)3)2]⁽¹⁺⁾*[ClO₄]^(1-)=[Au(P(C₆H₁₁)3)2][ClO₄] 

Relevant academic research and scientific papers

Dinuclear Au(I), Au(II) and Au(III) Complexes with (CF2)n Chains: Insights into The Role of Aurophilic Interactions in the Au(I) Oxidation

New dinuclear Au(I), Au(II) and Au(III) complexes containing (CF2)n bridging chains were obtained. Metallomacrocycles [Au2{μ-(CF2)4}{μ-diphosphine}] show an uncommon figure-eight structure, the helicity inversion barrier of which is influenced by aurophilic interactions and steric constraints imposed by the diphosphine. Halogenation of LAu(CF2)4AuL (L=PPh3, PMe3, (dppf)1/2, (binap)1/2) gave [Au(II)]2 species, some of which display unprecedented folded structures with Au?Au bonds. Aurophilic interactions facilitate this oxidation process by preorganizing the starting [Au(I)]2 complexes and lowering its redox potential. The obtained [Au(II)]2 complexes undergo thermal or photochemical elimination of R3PAuX to give Au(III) perfluorinated auracycles. Evidence of a radical mechanism for these decomposition reactions was obtained.

Neutral R3PAuGe9(Hyp)3 (R=Et, nPr, iPr, nBu, tBu, Cy) (Hyp=Si(SiMe3) Clusters give new insights into the ligand strength of the metalloid [Ge9(Hyp)3]? cluster

We present new insights into the ligand strength of the metalloid [Ge9(Hyp)3]? cluster (Hyp=Si(SiMe3)3) alongside novel neutral Ge9 clusters of the composition R3PAuGe9(Hyp)3 (R=Et, nPr, iPr, nBu, tBu, Cy). These clusters are synthesized in good yields from KGe9(Hyp)3 and R3PAuCl. Further experiments with these new clusters show that the ligand strength of [Ge9(Hyp)3]? is in between aryl and alkyl phosphines.

The leaving group in Au(i)-phosphine compounds dictates cytotoxic pathways in CEM leukemia cells and reactivity towards a Cys2His2model zinc finger

Gold(i)-phosphine auranofin-like compounds have been extensively explored as anticancer agents in the past decade. Although potent cytotoxic agents, the lack of selectivity towards tumorigenic vs. non-tumorigenic cell lines often hinders further application. Here we explore the cytotoxic effects of a series of (R3P)AuL compounds, evaluating both the effect of the basicity and bulkiness of the carrier phosphine (R = Et or Cy), and the leaving group L (Cl-vs. dmap). [Au(dmap)(Et3P)]+ had an IC50 of 0.32 μM against the CEM cell line, with good selectivity in relation to HUVEC. Flow cytometry indicates reduced G1 population and slight accumulation in G2, as opposed to auranofin, which induces a high population of cells with fragmented DNA. Protein expression profile sets [Au(dmap)(Et3P)]+ further apart from auranofin, with proteolytic degradation of caspase-3 and poly(ADP-ribose)-polymerase (PARP), DNA strand-break induced phosphorylation of Chk2 Thr68 and increased p53 ser15 phosphorylation. The cytoxicity and observable biological effects correlate directly with the reactivity trend observed when using the series of gold(i)-phosphine compounds for targeting a model zinc finger, Sp1 ZnF3.

Gold(I) complexes with chloro(diaryl)silyl ligand. Stoichiometric reactions and catalysis for O-functionalization of organosilane

An Au(I) complex with a chloro(diphenyl)silyl ligand [Au(SiPh2Cl)(PCy3)] (1a) is obtained from the reaction of Ph2SiH2 with [AuCl(PCy3)]. (4-FC6H4)2SiH2, (4-MeC6H4)2SiH2, and Ph2GeH2 react with [AuCl(PCy3)] to form complexes with the chlorodiarylsilyl ligand, [Au(SiAr2Cl)(PCy3)] (1b: Ar = C6H4-4-F, 1c: Ar = C6H4-4-Me) and with the chloro(diphenyl)germyl ligand, [Au(GePh2Cl)(PCy3)] (2a), respectively. Complex 1a reacts with H2O to form Ph2SiH(OH) and (Ph2SiH)2O, whereas the reaction of EtOH with 1a yields Ph2SiH(OEt) exclusively. Complex 1a catalyzes the hydrolysis of Ph2SiH2 ([Au]:[H2SiPh2]:[H2O] = 0.05:1.0:10.0) at 60 °C to yield Ph2SiH(OH) and (Ph2SiH)2O. The reaction of Ph2SiH2 with HOEt in the presence of a catalytic amount of 1a affords Ph2SiH(OEt). Both stoichiometric and catalytic reactions using 1a lead to the recovery of [AuCl(PCy3)] from the reaction mixture.

C(sp2)-C(sp2) Reductive Elimination from Well-Defined Diarylgold(III) Complexes

A series of well-defined phosphine-ligated diarylgold(III) complexes cis-[Au(L)(ArF)(Ar′)(Cl)] were prepared, and detailed kinetics of the C(sp2)-C(sp2) reductive elimination from these complexes were studied. The mechanism of the reductive elimination from the complexes cis-[Au(L)(ArF)(Ar′)(Cl)] was further studied by theoretical calculations. The combination of experimental and theoretical results suggests that the biaryl reductive elimination from organogold(III) complexes cis-[Au(L)(ArF)(Ar′)(Cl)] proceeds through a concerted biaryl-forming pathway from the four-coordinated Au(III) metal center. These studies also disclose that the steric hindrance of the phosphine ligands plays a major role in promoting the biaryl-forming reductive elimination from diarylgold(III) complexes cis-[Au(L)(ArF)(Ar′)(Cl)], while electronic properties of these ligands have a much smaller effect. Futhermore, it was found that the complexes with more weakly electron withdrawing aryl ligands undergo reductive elimination more quickly and the elimination rate is not sensitive to the polarity of the solvents.

Probing the HIV-1 NCp7 Nucleocapsid Protein with Site-Specific Gold(I)-Phosphine Complexes

In this work, we examined a series of thiophilic Au(I) compounds based on [Au(L)(PR3)] (L = Cl-, 4-dimethylaminopyridine (dmap); R= ethyl (Et), cyclohexyl (Cy)) for chemoselective auration of the C-terminal HIV nucleocapsid protein NCp7 F2 and the full HIV NCp7 (NC, zinc finger (ZnF)) as probes of nucleocapsid topography. The choice of phosphine allowed electronic and steric effects to be considered. The use of the heterocycle leaving group allowed us to study the effect of possible π-stacking with the essential tryptophan residue of NC on the reactivity and selectivity, mimicking the naturally occurring interaction between the zinc finger and nucleic acids. We also examined for comparison the standard gold-phosphine compound auranofin, which contains an S-bound glucose coordinated to the {Au(PEt3)} moiety. Both the nature of the phosphine and the nature of L affect the reactivity with the C-terminal NCp7 F2 and the full NC. 31P NMR spectroscopy showed the formation of long-lived {Au(PR3)}-ZnF species in all cases, but in the case of NCp7 F2, a selective interaction in the presence of the dmap ligand was observed. In the case of auranofin, an unusual Au-His (rather than Au-Cys) coordination was indicated on NC. The overall results suggest that it is useful to consider three aspects of zinc finger structure in considering the profile of chemical reactivity: (i) the zinc-bound cysteines as primary nucleophiles; (ii) the zinc-bound histidine as a spectator ligand; and (iii) ancillary groups not bound to Zn but essential for ZnF function such as the essential tryptophan in NCp7 F2 and NC. Modification of fully functional NC zinc finger by the Cy3P-containing species confirmed the inhibition of the NC-SL2 DNA interaction, as evaluated by fluorescence polarization.

Photosensitizer-Free, Gold-Catalyzed C–C Cross-Coupling of Boronic Acids and Diazonium Salts Enabled by Visible Light

The first photosensitizer-free visible light-driven, gold-catalyzed C–C cross-couplings of arylboronic acids and aryldiazonium salts are reported. The reactions can be conducted under very mild conditions, using a catalytic amount of tris(4-trifluoromethyl)phosphinegold(I) chloride [(4-CF3-C6H4)3PAuCl] with methanol as the solvent allowing an alternative access to a variety of substituted biaryls in moderate to excellent yields with broad functional group tolerance. (Figure presented.).

Induced Circular Dichroism in Phosphine Gold(I) Aryl Acetylide Urea Complexes through Hydrogen-Bonded Chiral Co-Assemblies

Phosphine gold(I) aryl acetylide complexes equipped with a central bis(urea) moiety form 1D hydrogen-bonded polymeric assemblies in solution that do not display any optical activity. Chiral co-assemblies are formed by simple addition of an enantiopure (metal-free) complementary monomer. Although exhibiting an intrinsically achiral linear geometry, the gold(I) aryl acetylide fragment is located in the chiral environment displayed by the hydrogen-bonded co-assemblies, as demonstrated by induced circular dichroism (ICD). Phosphine gold(I) aryl acetylide complexes equipped with a central bis(urea) moiety form hydrogen-bonded supramolecular polymers in solution that do not display any optical activity. Co-assembly with a chiral (metal-free) co-monomer is used to place the intrinsically achiral gold(I) aryl acetylide fragment in a chiral environment, as demonstrated by induced circular dichroism (ICD).

Alkyne Difunctionalization by Dual Gold/Photoredox Catalysis

Highly selective tandem nucleophilic addition/cross-coupling reactions of alkynes have been developed using visible-light-promoted dual gold/photoredox catalysis. The simultaneous oxidation of AuI and coordination of the coupling partner by photo-generated aryl radicals, and the use of catalytically inactive gold precatalysts allows for high levels of selectivity for the cross-coupled products without competing hydrofunctionalization or homocoupling. As demonstrated in representative arylative Meyer-Schuster and hydration reactions, this work expands the scope of dual gold/photoredox catalysis to the largest class of substrates for gold catalysts and benefits from the mild and environmentally attractive nature of visible-light activation. United we stand! Tandem nucleophilic addition/cross-coupling reactions have been developed with challenging alkynes using a visible-light-promoted dual gold/photoredox catalytic system (see scheme). High levels of selectivity for the cross-coupled products were obtained without competition from the homocoupling or conventional hydrofunctionalization.

Oxidative Addition to Gold(I) by Photoredox Catalysis: Straightforward Access to Diverse (C,N)-Cyclometalated Gold(III) Complexes

Herein, we report the oxidative addition of aryldiazonium salts to ligand-supported gold(I) complexes under visible light photoredox conditions. This method provides experimental evidence for the involvement of such a process in dual gold/photoredox-catalyzed reactions and delivers well-defined (C,N)-cyclometalated gold(III) species. The remarkably mild reaction conditions and the ability to widely vary the ancillary ligand make this method a potentially powerful synthetic tool to access diverse gold(III) complexes for systematic studies into their properties and reactivity. Initial studies show that these species can undergo chloride abstraction to afford Lewis acidic dicationic gold(III) species.