96029-36-6

Upstream product

• 855-38-9 P(p-CH₃OC₆H₄)3 
• 1254985-79-9 chloro(dimethyl sulfide)gold(I) 
• 29892-37-3 chloro(dimethylsulfide) gold(I) 
• 10294-29-8 gold(I) chloride 
• 39929-21-0 (tetrahydrothiophene)gold(I) chloride 

Downstream Products

• 103334-80-1 [(Au(P(C₆H₄OCH₃)3))2(CC)] 
• 201612-31-9 Au₂(C₃S₄Se)(P(C₆H₄OCH₃)3)2 
• 204252-47-1 μ-(2-thioxo-1,3-dithiole-4,5-dithiolato)bis[(tris(p-methoxyphenyl)phosphine)gold(I)] 
• 1094064-61-5 ((p-MeOC₆H₄)3P)Au(C₄HO(O)(CH₃)(n-C₆H₁₃)) 
• 1371611-48-1 [((4-methoxyphenyl)3P)AuCCC₆H₄-4-NHC(O)NHC₆H₅] 
• 1371611-50-5 [((4-methoxyphenyl)3P)AuCCC₆H₄-4-NHC(O)NHC₆H₄-4-OCH₃] 
• 186884-24-2 [AuBr{tris((4-methoxyphenyl)phosphine)₃}] 

Relevant academic research and scientific papers

Reversible Covalent and Supramolecular Functionalization of Water-Soluble Gold(I) Complexes

The ligation of gold(I) metalloamphiphiles with biomolecules is reported, using water-soluble AuI-N-alkynyl substituted maleimide complexes. For this purpose, two different polar ligands were applied: 1) a neutral, dendritic tetraethylene glycol-functionalized phosphane and 2) a charged, sulfonated N-heterocyclic carbene (NHC). The retro Diels–Alder reaction of a furan-protected maleimide gold(I) complex, followed by cycloaddition with a diene-functionalized biotin under mild conditions leads to a novel gold(I) metalloamphiphile. The strong streptavidin–biotin binding affinity in buffered aqueous solution of the resulting biotin alkynyl gold(I) phosphane conjugate remains intact. The cytotoxicity of the biotinylated gold(I) complex against a T47D human breast cancer cell line is higher than for cisplatin.

Au(I)-Catalyzed Oxidative Functionalization of Yndiamides

Yndiamides, underexplored cousins of ynamides, offer rich synthetic potential as doubly nitrogenated two carbon building blocks. Here we report a gold-catalyzed oxidative functionalization of yndiamides to access unnatural amino acid derivatives, using a wide range of nucleophiles as a source of the amino acid side chain. The transformation proceeds under mild conditions, is highly functional group tolerant, and displays excellent regioselectivity through subtle steric differentiation of the yndiamide nitrogen atom substituents.

Synthesis of L-Au(I)-CF2H Complexes and Their Application as Transmetalation Shuttles to the Difluoromethylation of Aryl Iodides

We describe herein two alternative protocols to efficiently prepare difluoromethylgold(I) complexes bearing ancillary ligands with different electronic and steric properties. LAu-OX (X = H andt-Bu) species, formed in the presence of base, have been identified as intermediate complexes involved in these transformations. The application of these compounds as “CF2H transmetalation shuttles” from gold to palladium has been demonstrated in a Pd-catalyzed difluoromethylation reaction of aryl iodides, in which the Au-to-Pd transfer of “CF2H” is feasible under stoichiometric conditions. These findings will pave the way for catalytic manifolds in gold chemistry.

Systematically Tuning the Electronic Structure of Gold Nanoclusters through Ligand Derivatization

While the ability to crystallize metal nanoclusters has revealed their geometric structure, the lack of a similarly precise measure of their electronic structure has hampered the development of synthetic design rules to precisely engineer their electronic properties. We track the evolution of highly-resolved electronic absorption spectra of gold nanoclusters with precisely mass-selected chemical composition in a controlled environment. Simple derivatization of the ligands yields larger spectral changes than varying the overall atomic composition of the cluster for two clusters with similar symmetry and size. The nominally metal-localized HOMO–LUMO transition of these nanoclusters lowers in energy linearly with increasing electron donation from the exterior of the ligand shell for both cluster sizes. Very weak surface interactions, such as binding of He or N2, yield significant state-dependent shifts, identifying states with significant interfacial character. These observations demonstrate a pathway for deliberate tuning of interfacial chemistry for chemical and technological applications.

Synthesis and Structure-Activity Relationship Study of Antimicrobial Auranofin against ESKAPE Pathogens

Auranofin, an FDA-approved arthritis drug, has recently been repurposed as a potential antimicrobial agent; it performed well against many Gram-positive bacteria, including multidrug resistant strains. It is, however, inactive toward Gram-negative bacteria, for which we are in dire need of new therapies. In this work, 40 auranofin analogues were synthesized by varying the structures of the thiol and phosphine ligands, and their activities were tested against ESKAPE pathogens. The study identified compounds that exhibited bacterial inhibition (MIC) and killing (MBC) activities up to 65 folds higher than that of auranofin, making them effective against Gram-negative pathogens. Both thiol and the phosphine structures influence the activities of the analogues. The trimethylphosphine and triethylphosphine ligands gave the highest activities against Gram-negative and Gram-positive bacteria, respectively. Our SAR study revealed that the thiol ligand is also very important, the structure of which can modulate the activities of the AuI complexes for both Gram-negative and Gram-positive bacteria. Moreover, these analogues had mammalian cell toxicities either similar to or lower than that of auranofin.

Gold(i) and gold(iii) phosphine complexes: synthesis, anticancer activities towards 2D and 3D cancer models, and apoptosis inducing properties

A series of gold(i), gold(iii) and cationic gold(i) complexes of tris(4-methoxyphenyl)phosphine and tris(2,6-dimethoxyphenyl)phosphine were synthesised and fully characterised by spectroscopic methods. The molecular structures of selected complexes were also determined by X-ray diffraction analysis. The prepared complexes [AuX{P(C6H4-4-OMe)3}] [X = Cl (1), Br (2), I (3)], [AuCl3{P(C6H4-4-OMe)3}] (4), [Au{P(C6H4-4-OMe)3}2]PF6 (5), [AuX{P(C6H3-2,6-{OMe}2)3}] [X = Cl (6), Br (7), I (8)], [AuCl3{P(C6H3-2,6-{OMe}2)3}] (9) and [Au{P(C6H3-2,6-{OMe}2)3}2]PF6 (10) were investigated for their anticancer activity against five human tumor cell lines [ovarian (SKOV-3), fibrosarcoma (HT1080), glioblastoma (U87MG), prostate (PC-3), and cervical (HeLa)] as well as against 3D spheroidal models of HeLa cells. The cationic complex 10 was found to exhibit a remarkably broad spectrum of anticancer activity with approximately 30-fold higher toxicity than cisplatin against PC-3 and U87MG cancer cells; this complex also showed the strongest inhibition of spheroid growth in 3D models of HeLa cells. The mechanism of anticancer activity of these gold complexes was found to be strong inhibition of thioredoxin reductase, increased ROS production and subsequent apoptosis induction as evidenced by the sub G1 cell accumulation, DNA fragmentation, and caspase-3 activation.

Oxidative 1,2-Difunctionalization of Ethylene via Gold-Catalyzed Oxyarylation

Under the conditions of oxidative gold catalysis, exposure of ethylene to aryl silanes and alcohols generates products of 1,2-oxyarylation. This provides a rare example of a process that allows catalytic differential 1,2-difunctionalization of this feedstock chemical.

Synthesis of Substituted Quinolizidines via a Gold-Catalyzed Double Cyclization Cascade

A novel synthesis of quinolizidines by a cationic gold-catalyzed double cyclization cascade has been developed. The reaction was initiated by the gold-catalyzed 6-exo-dig cyclization of ynamides, which was followed by a second cyclization of an enamide intermediate to provide the corresponding quinolizidine derivatives. The utility of this reaction was demonstrated by application to the synthesis of multi-substituted quinolizidines and by the total synthesis of a quinolizidine alkaloid, (±)-lupinine.

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.