Tag: 600-700

《Enantioselective Synthesis of Planar Chiral Zigzag-Type Cyclophenylene Belts by Rhodium-Catalyzed Alkyne Cyclotrimerization》 was written by Nogami, Juntaro; Tanaka, Yusuke; Sugiyama, Haruki; Uekusa, Hidehiro; Muranaka, Atsuya; Uchiyama, Masanobu; Tanaka, Ken. Computed Properties of C38H28O4P2This research focused onzigzag cyclophenylene belt enantioselective preparation; rhodium catalyst enantioselective cyclotrimerization heptynyl oxypropynylphenoxyphenylene oligomer; mol crystal structure racemic zigzag cyclophenylene belt; mechanism enantioselectivity cyclotrimerization heptynyl oxypropynylphenoxyphenylene; ring strain calculated zigzag cyclophenylene belt; fluorescence UV visible absorption zigzag cyclophenylene belt; dissymetry factor ECD CPL nonracemic zigzag cyclophenylene belt. The article conveys some information:

Planar chiral zigzag-type [8] and [12]cyclophenylene belts were prepared enantioselectively by rhodium-catalyzed enantioselective intramol. sequential cyclotrimerizations of a cyclic [oxypropynylbis(heptynyloxy)phenoxybis(heptynyl)phenylene] dimer and trimer. The observed enantioselectivity likely arose from the regioselective formation of a rhodacyclic intermediate from an unsym. triyne unit. The structure of the racemic zigzag [8]cyclophenylene belt was determined by X-ray crystallog.; the homochiral belts mesh with one another to form columns in the solid state, with columns of alternating chiralities. The ring strain of the zigzag [8]cyclophenylene belt was smaller than that of the corresponding armchair-type cycloparaphenylene despite its smaller ring size because of the presence of strain-relieving m-terphenyl moieties. The effect of the number of the benzene rings in the zigzag cyclophenylene belts on their UV/visible absorption and fluorescence was small because of the interruption of conjugation by the m-phenylene moieties, but the effect of bending on the absorption and emission peaks and on the absolute fluorescence quantum yield was significant. Modest anisotropy dissymmetry factors of the electronic CD and CPL spectra were observed for the zigzag [8]cyclophenylene belt. The results came from multiple reactions, including the reaction of (S)-5,5′-Bis(diphenylphosphino)-4,4′-bi-1,3-benzodioxole(cas: 210169-54-3Computed Properties of C38H28O4P2)

(S)-5,5′-Bis(diphenylphosphino)-4,4′-bi-1,3-benzodioxole(cas: 210169-54-3) may be used for: regio- and stereoselective preparation of axially chiral arylnaphthalene derivatives via rhodium-catalyzed [2+2+2] cycloaddition of diynes with naphthalenepropynoic acid derivatives or diastereo- and enantioselective hydrogenation of α-amino-β-keto ester hydrochlorides catalyzed by an iridium complex.Computed Properties of C38H28O4P2

Referemce:
Phosphine ligand,
Chiral phosphines in nucleophilic organocatalysis

Application In Synthesis of (S)-5,5′-Bis(diphenylphosphino)-4,4′-bi-1,3-benzodioxoleIn 2021 ,《Computational and Experimental Insights into Asymmetric Rh-Catalyzed Hydrocarboxylation with CO2》 was published in European Journal of Organic Chemistry. The article was written by Pavlovic, Ljiljana; Pettersen, Martin; Gevorgyan, Ashot; Vaitla, Janakiram; Bayer, Annette; Hopmann, Kathrin H.. The article contains the following contents:

The asym. Rh-catalyzed hydrocarboxylation of α,β-unsaturated carbonyl compounds was originally developed by Mikami and co-workers but gives only moderate enantiomeric excesses. In order to understand the factors controlling the enantioselectivity and to propose novel ligands for this reaction, we have used computational and exptl. methods to study the Rh-catalyzed hydrocarboxylation with different bidentate ligands. The anal. of the C-CO2 bond formation transition states with DFT methods shows a preference for outer-sphere CO2 insertion, where CO2 can undergo a backside or frontside reaction with the nucleophile. The two ligands that prefer a frontside reaction, StackPhos and tBu-BOX, display an intriguing stacking interaction between CO2 and an N-heterocyclic ring of the ligand (imidazole or oxazoline). Our exptl. results support the computationally predicted low enantiomeric excesses and highlight the difficulty in developing a highly selective version of this reaction. The experimental part of the paper was very detailed, including the reaction process of (S)-5,5′-Bis(diphenylphosphino)-4,4′-bi-1,3-benzodioxole(cas: 210169-54-3Application In Synthesis of (S)-5,5′-Bis(diphenylphosphino)-4,4′-bi-1,3-benzodioxole)

(S)-5,5′-Bis(diphenylphosphino)-4,4′-bi-1,3-benzodioxole(cas: 210169-54-3) is a chelating ligand used to prepare coordination complex catalysts, such as its use in Pd catalysts for the enantioselective synthesis of spiro- or benzofused hetereocycles with exocyclic olefins via enantioselective intramolecular dearomative Heck reaction of indoles, benzofurans, pyrroles and furans.Application In Synthesis of (S)-5,5′-Bis(diphenylphosphino)-4,4′-bi-1,3-benzodioxole

Referemce:
Phosphine ligand,
Chiral phosphines in nucleophilic organocatalysis

In 2022,Zhu, Jian-Xiang; Chen, Zhi-Chao; Du, Wei; Chen, Ying-Chun published an article in Angewandte Chemie, International Edition. The title of the article was 《Asymmetric Auto-Tandem Palladium Catalysis for 2,4-Dienyl Carbonates: Ligand-Controlled Divergent Synthesis》.COA of Formula: C38H28O4P2 The author mentioned the following in the article:

Herein a palladium-catalyzed auto-tandem reaction between 2,4-dienyl carbonates and o-TsNH arylimines or trifluoroacetophenones was presented, that proceeded through a consecutive N-allylation, vinylogous addition, π-σ-π isomerization, and another N-allylation sequence. Importantly, switchable diastereodivergent synthesis could be achieved by tuning the chiral bisphosphine ligands, which led to the construction of a broad spectrum of fused tetrahydroquinoline architectures such as I [R1 = H, 4-Me, 5-Cl, etc.; R2 = Ms, Ts, SO2(2-thienyl); R3 = Me, Ph, 2-furyl, etc.] with moderate to excellent enantioselectivity. Ligand control even enabled effective access to regiodivergent azetidines or chemodivergent β-H elimination with fair enantioselectivity, further showing the versatility of the current auto-tandem catalysis.(S)-5,5′-Bis(diphenylphosphino)-4,4′-bi-1,3-benzodioxole(cas: 210169-54-3COA of Formula: C38H28O4P2) was used in this study.

(S)-5,5′-Bis(diphenylphosphino)-4,4′-bi-1,3-benzodioxole(cas: 210169-54-3) may be used for: regio- and stereoselective preparation of axially chiral arylnaphthalene derivatives via rhodium-catalyzed [2+2+2] cycloaddition of diynes with naphthalenepropynoic acid derivatives or diastereo- and enantioselective hydrogenation of α-amino-β-keto ester hydrochlorides catalyzed by an iridium complex.COA of Formula: C38H28O4P2

Referemce:
Phosphine ligand,
Chiral phosphines in nucleophilic organocatalysis

Bernardo, Olaya; Gonzalez-Pelayo, Silvia; Fernandez, Israel; Lopez, Luis A. published an article in 2021. The article was titled 《Gold-Catalyzed Reaction of Propargyl Esters and Alkynylsilanes: Synthesis of Vinylallene Derivatives through a Twofold 1,2-Rearrangement》, and you may find the article in Angewandte Chemie, International Edition.Category: chiral-phosphine-ligands The information in the text is summarized as follows:

The reaction of propargyl esters with alkynylsilanes under gold catalysis provides vinylallene derivatives through consecutive [1,2]-acyloxy/[1,2]-silyl rearrangements. Good yields, full atom-economy, broad substrate scope, easy scale-up and low catalyst loadings are salient features of this novel transformation. D. Functional Theory (DFT) calculations suggest a reaction mechanism involving initial [1,2]-acyloxy rearrangement to generate a gold vinylcarbene intermediate which upon regioselective attack of the alkynylsilane affords a vinyl cation which undergoes a type II-dyotropic rearrangement involving the silyl group and the metal fragment. Preliminary results on the enantioselective version of this transformation are also disclosed. The results came from multiple reactions, including the reaction of (S)-5,5′-Bis(diphenylphosphino)-4,4′-bi-1,3-benzodioxole(cas: 210169-54-3Category: chiral-phosphine-ligands)

(S)-5,5′-Bis(diphenylphosphino)-4,4′-bi-1,3-benzodioxole(cas: 210169-54-3) is a chelating ligand used to prepare coordination complex catalysts, such as its use in Pd catalysts for the enantioselective synthesis of spiro- or benzofused hetereocycles with exocyclic olefins via enantioselective intramolecular dearomative Heck reaction of indoles, benzofurans, pyrroles and furans.Category: chiral-phosphine-ligands

Referemce:
Phosphine ligand,
Chiral phosphines in nucleophilic organocatalysis

Miyamoto, Yukiko;Aggarwal, Shubhangi;Celaje, Jeff Joseph A.;Ihara, Sozaburo;Ang, Jonathan;Eremin, Dmitry B.;Land, Kirkwood M.;Wrischnik, Lisa A.;Zhang, Liangfang;Fokin, Valery V.;Eckmann, Lars published 《Gold(I) Phosphine Derivatives with Improved Selectivity as Topically Active Drug Leads to Overcome 5-Nitroheterocyclic Drug Resistance in Trichomonas vaginalis》 in 2021. The article was appeared in 《Journal of Medicinal Chemistry》. They have made some progress in their research.Electric Literature of C20H36AuO9PS The article mentions the following:

Trichomonas vaginalis causes the most common, nonviral sexually transmitted infection. Only metronidazole (Mz) and tinidazole are approved for treating trichomoniasis, yet resistance is a clin. problem. The gold(I) complex, auranofin, is active against T. vaginalis and other protozoa but has significant human toxicity. In a systematic structure-activity exploration, authors show here that diversification of gold(I) complexes, particularly as halides with simple C1-C3 trialkyl phosphines or as bistrialkyl phosphine complexes, can markedly improve potency against T. vaginalis and selectivity over human cells compared to that of the existing antirheumatic gold(I) drugs. All gold(I) complexes inhibited the two most abundant isoforms of the presumed target enzyme, thioredoxin reductase, but a subset of compounds were markedly more active against live T. vaginalis than the enzyme, suggesting that alternative targets exist. Furthermore, all tested gold(I) complexes acted independently of Mz and were able to overcome Mz resistance, making them candidates for the treatment of Mz-refractory trichomoniasis. And ((2S,3R,4S,5R,6R)-3,4,5-Triacetoxy-6-(acetoxymethyl)tetrahydro-2H-pyran-2-thio)(triethylphosphine)gold (cas: 34031-32-8) was used in the research process.

((2S,3R,4S,5R,6R)-3,4,5-Triacetoxy-6-(acetoxymethyl)tetrahydro-2H-pyran-2-thio)(triethylphosphine)gold(cas: 34031-32-8) is a gold(I)-phosphine thiolate small molecule described to produce antiinflammatory and antiarthritic effects.Electric Literature of C20H36AuO9PS

Reference:
Phosphine ligand,
Chiral phosphines in nucleophilic organocatalysis

Wang, Guosong;Chen, Ruiqi;Huang, Pengfei;Hong, Junping;Cao, Jiali;Wu, Qian;Zheng, Wei;Lin, Lina;Han, Qiangyuan;Chen, Yixin;Xia, Ningshao published 《Adefovir dipivoxil efficiently inhibits the proliferation of pseudorabies virus in vitro and in vivo》. The research results were published in《Antiviral Research》 in 2021.Synthetic Route of C20H36AuO9PS The article conveys some information:

Since 2011, highly pathogenic pseudorabies virus (PRV) variants that emerged on many farms in China have posed major economic burdens to the animal industry and have even recently caused several human cases of viral encephalitis. Currently, there are no approved effective drugs to treat PRV associated diseases in humans or pigs. Thus, it is important to develop a new effective drug for the treatment of PRV infection. To this end, we established a novel rapid method to screen drugs against PRV from 1818 kinds of small mol. drugs approved by the FDA. Using this method, we identified 21 kinds of them that can strongly suppress the proliferation of PRV. Mitoxantrone, puromycin dihydrochloride, mitoxantrone hydrochloride and adefovir dipivoxil effectively inhibited PRV in vitro. Of them, only adefovir dipivoxil could potently protect mice against lethal PRV infection. Our work identifies several kinds of potential therapeutics against PRV and may offer important guidance for controlling PRV epidemics and treating associated diseases in humans and animals. And ((2S,3R,4S,5R,6R)-3,4,5-Triacetoxy-6-(acetoxymethyl)tetrahydro-2H-pyran-2-thio)(triethylphosphine)gold (cas: 34031-32-8) was used in the research process.

((2S,3R,4S,5R,6R)-3,4,5-Triacetoxy-6-(acetoxymethyl)tetrahydro-2H-pyran-2-thio)(triethylphosphine)gold(cas: 34031-32-8) is a gold(I)-phosphine thiolate small molecule described to produce antiinflammatory and antiarthritic effects.Synthetic Route of C20H36AuO9PS

Reference:
Phosphine ligand,
Chiral phosphines in nucleophilic organocatalysis

Saha, Achinto;Zhao, Shengyuan;Chen, Zhao;Georgiou, George;Stone, Everett;Kidane, Dawit;DiGiovanni, John published 《Combinatorial Approaches to Enhance DNA Damage following Enzyme-Mediated Depletion of L-Cys for Treatment of Pancreatic Cancer》 in 2021. The article was appeared in 《Molecular Therapy》. They have made some progress in their research.Reference of ((2S,3R,4S,5R,6R)-3,4,5-Triacetoxy-6-(acetoxymethyl)tetrahydro-2H-pyran-2-thio)(triethylphosphine)gold The article mentions the following:

Pancreatic ductal adenocarcinoma (PDAC) represents one of the deadliest forms of cancer with very few available therapeutic options. We previously reported that an engineered human enzyme, cyst(e)inase, which degrades L-cysteine (L-Cys) and cystine, inhibits growth of multiple cancer cells, including PDAC both in vitro and in vivo. Here, we show that cyst(e)inase treatment leads to increased clustered oxidative DNA damage, DNA single-strand breaks, apurinic/apyrimidinic sites, and DNA double-strand breaks (DSBs) in PDAC cells sensitive to intracellular depletion of L-Cys that is associated with reduced survival. BRCA2-deficient PDAC cells exhibited increased DSBs and enhanced sensitivity to cyst(e)inase. The blocking of a second antioxidant pathway (thioredoxin/thioredoxin reductase) using auranofin or inhibiting DNA repair using the poly (ADP-ribose) polymerase (PARP) inhibitor, olaparib, led to significant increases in DSBs following cyst(e)inase treatment in all PDAC cells examined Cyst(e)inase plus olaparib also synergistically inhibited growth of sensitive and resistant PDAC cells in both xenograft and allograft tumor models. Collectively, these results demonstrate an important role for oxidative DNA damage and ultimately DNA DSBs in the anticancer action of cyst(e)inase. The data further show the potential for combining agents that target alternate antioxidant pathways or by targeting DNA repair pathways or genetic liabilities in DNA repair pathways to enhance the therapeutic action of cyst(e)inase for PDAC. The experimental procedure involved many compounds, such as ((2S,3R,4S,5R,6R)-3,4,5-Triacetoxy-6-(acetoxymethyl)tetrahydro-2H-pyran-2-thio)(triethylphosphine)gold (cas: 34031-32-8) .

((2S,3R,4S,5R,6R)-3,4,5-Triacetoxy-6-(acetoxymethyl)tetrahydro-2H-pyran-2-thio)(triethylphosphine)gold(cas: 34031-32-8) is a disease-modifying antirheumatic drug (DMARD) and has been used to study the anti-proliferative effects against OVCAR-3 human ovarian carcinoma cells.Reference of ((2S,3R,4S,5R,6R)-3,4,5-Triacetoxy-6-(acetoxymethyl)tetrahydro-2H-pyran-2-thio)(triethylphosphine)gold

Reference:
Phosphine ligand,
Chiral phosphines in nucleophilic organocatalysis

Yamashita, Masamichi published 《Auranofin: Past to Present, and repurposing》. The research results were published in《International Immunopharmacology》 in 2021.Safety of ((2S,3R,4S,5R,6R)-3,4,5-Triacetoxy-6-(acetoxymethyl)tetrahydro-2H-pyran-2-thio)(triethylphosphine)gold The article conveys some information:

Auranofin (AF), a gold compound, has been used to treat rheumatoid arthritis (RA) for more than 40 years; however, its mechanism of action remains unknown. We revealed that AF inhibited the induction of proinflammatory proteins and their mRNAs by the inflammatory stimulants, cyclooxygenase-2 and inducible nitric oxide synthase, and their upstream regulator, NF-κB. AF also activated the proteins peroxyredoxin-1, Kelch-like ECH-associated protein 1, and NF-E2-related factor 2, and inhibited thioredoxin reductase, all of which are involved in oxidative or electrophilic stress under physiol. conditions. Although the cell membrane was previously considered to be permeable to AF because of its hydrophobicity, the mechanisms responsible for transporting AF into and out of cells as well as its effects on the uptake and excretion of other drugs have not yet been elucidated. Antibodies for cytokines have recently been employed in the treatment of RA, which has had an impact on the use of AF. Trials to repurpose AF as a risk-controlled agent to treat cancers or infectious diseases, including severe acute respiratory syndrome coronavirus 2/coronavirus disease 2019, are ongoing. Novel gold compounds are also under development as anti-cancer and anti-infection agents.((2S,3R,4S,5R,6R)-3,4,5-Triacetoxy-6-(acetoxymethyl)tetrahydro-2H-pyran-2-thio)(triethylphosphine)gold (cas: 34031-32-8) were involved in the experimental procedure.

((2S,3R,4S,5R,6R)-3,4,5-Triacetoxy-6-(acetoxymethyl)tetrahydro-2H-pyran-2-thio)(triethylphosphine)gold(cas: 34031-32-8) is an efficient inducer of mitochondrial membrane permeability transition pore in the presence of calcium ions related to its inhibition of mitochondrial thioredoxin reductase.Safety of ((2S,3R,4S,5R,6R)-3,4,5-Triacetoxy-6-(acetoxymethyl)tetrahydro-2H-pyran-2-thio)(triethylphosphine)gold

Reference:
Phosphine ligand,
Chiral phosphines in nucleophilic organocatalysis

Formula: C20H36AuO9PS《Inhibition of thioredoxin reductase (TrxR) triggers oxidative stress-induced apoptosis in filarial nematode Setaria cervi channelized through ASK-1-p38 mediated caspase activation》 was published in 2021. The authors were Joardar, Nikhilesh;Sen, Animesh;Rath, Jnanendra;Babu, Santi P. Sinha, and the article was included in《Molecular & Biochemical Parasitology》. The author mentioned the following in the article:

Inhibition of an imperative antioxidant enzyme with subsequent death is a victorious and widely accepted strategy to combat various infectious diseases. Among different antioxidant enzymes, thioredoxin reductase (TrxR) is an exclusive one. Studies have revealed that direct inhibition of TrxR by different classes of chem. moieties promptly results in the death of an organism. Especially the structural as well as biochem. modifications of the enzyme upon inhibition project serious threat towards the subject organism. Herein, an attempt was made to inhibit TrxR of filarial species by administering Auranofin, 1 chloro 2,4 dinitrobenzene (CDNB), Curcumin, and a novel carbamo dithioperoxo(thioate) derivative (4a). Our study has revealed that inhibition of TrxR resulted in the induction of the classical CED pathway of apoptosis along with the intrinsic and extrinsic pathways of apoptosis (Caspase mediated) routed through the ASK-1/p38 axis. Druggability anal. of filarial TrxR for the selected compounds was performed in silico through mol. docking studies. Therefore, this study attempts to decipher the mechanism of apoptosis induction following TrxR inhibition. The safety of those four compounds in terms of dose and toxicity was taken under consideration. Thitherto, the mechanism of TrxR mediated initiation of cell death in filarial parasite has remained undercover, and therefore, it is a maiden report on the characterization of apoptosis induction upon TrxR inhibition which will eventually help in generating effective antifilarial drugs in the future. To complete the study, the researchers used ((2S,3R,4S,5R,6R)-3,4,5-Triacetoxy-6-(acetoxymethyl)tetrahydro-2H-pyran-2-thio)(triethylphosphine)gold (cas: 34031-32-8) .

((2S,3R,4S,5R,6R)-3,4,5-Triacetoxy-6-(acetoxymethyl)tetrahydro-2H-pyran-2-thio)(triethylphosphine)gold(cas: 34031-32-8) is a disease-modifying antirheumatic drug (DMARD) and has been used to study the anti-proliferative effects against OVCAR-3 human ovarian carcinoma cells.Formula: C20H36AuO9PS

Reference:
Phosphine ligand,
Chiral phosphines in nucleophilic organocatalysis