10.1016/S0008-6215(00)85248-9
A study detailing the synthesis of a glycotripeptide and a glycosomatostatin, both containing the 3-O-(2-acetamido-2-deoxy-D-glucopyranosyl)-L-serine residue. The research was conducted by a team from the Salk Institute for Biological Studies and the University of California, San Diego. The process involved solid-phase synthesis to create the sequences Gly-[P-D-GlcpNAc-(1→3)-Ser]-Ala-OH and /I-D-GlcpNAc-(1→3)-Ser-13-somatostatin. The synthesized glycopeptides were found to be homogeneous upon examination through thin-layer chromatography (t.l.c.) and liquid chromatography (l.c.), and they exhibited the correct amino acid composition and 2-amino-2-deoxy-D-glucose content. The structure of one of the glycopeptides was confirmed by mass spectrometry and nuclear magnetic resonance (n.m.r.) spectroscopy. The study was supported by grants from the National Institute of Arthritis, Metabolism, and Digestive Diseases, the National Heart Institute, and the William Randolph Hearst Foundation, among others.
10.1021/om100819q
The research focuses on the synthesis and characterization of a heteroleptic palladium(II) complex containing a bidentate carbene/amido ligand and 3-(trifluoromethyl)-5-(2-pyridyl)pyrazolate, which serves as an efficient catalyst in the Heck coupling reaction. The experiments involve a multicomponent reaction between PdCl2, fppzH, and [LH1H2]Cl in the presence of K2CO3 to prepare PdL(fppz) with good yield. The synthesized palladium and platinum complexes were characterized using 1D and 2D NMR spectroscopy, X-ray crystallography, electrospray ionization mass spectrometry, and elemental analyses. X-ray photoelectron spectroscopy was also employed to indicate the electron richness of the palladium atoms in PdL(fppz). The catalytic performance of the complexes was evaluated in Heck coupling reactions with various aryl halides and alkenes, using conditions such as light palladium loading, temperature, and microwave heating to optimize the reaction yields and activation times.
10.1039/c1ob05862b
The study presents a novel synthetic approach to the C19 methyl ether of aspercyclide A, a natural product antagonist of the human IgE-FceRI protein-protein interaction, which is a key component in the signal transduction pathway for allergic disorders such as asthma. The synthesis involves a Pd(0)-catalyzed, fluorous-tagged alkenylgermane/arylbromide macrocyclisation (germyl-Stille reaction) as the key step, followed by an evaluation of both enantiomers of the compound via ELISA after optical resolution by CSP-HPLC. The chemicals used in the study include alkenylgermane, arylbromide, palladium catalysts, fluorous tags for purification, and various reagents for the macrocyclisation and enantiomer separation processes. These chemicals serve the purpose of constructing the complex macrocyclic structure of aspercyclide A C19 methyl ether and assessing its potential as an anti-asthma therapeutic by evaluating its binding affinity to the IgE-FceRI protein interaction.
10.1016/j.molcata.2010.06.026
The research focused on the synthesis and evaluation of palladium complexes with macromolecular o-trifluoromethylphenyl-substituted phosphine ligands for their catalytic performance in hydroxycarbonylation and alkoxycarbonylation of olefins. The aim of the study was to evaluate the influence of steric and electronic effects on the coordination ability of the ligands and to develop highly regioselective catalysts for these carbonylation reactions. The researchers synthesized and characterized palladium complexes with tert-butyl and o-trifluoromethylphenyl substituents and compared their performance with that of triphenylphosphine and tricyclohexylphosphine. It was concluded that the palladium complex of tert-butyl(o-trifluoromethylphenyl)methylphosphine (complex 12) exhibited extremely high regioselectivity and good yields in the hydroxy and alkoxycarbonylation of a range of vinyl aromatics, surpassing the performance of traditionally used triphenylphosphine-based catalysts. This finding suggests that these macromolecular phosphine ligands may help achieve more efficient and selective carbonylation reactions in organic synthesis.
10.1021/acs.orglett.0c01488
The research focuses on the development of new amide precursors for the selective and catalytic activation of carbon-nitrogen bonds in amides, a fundamental objective in the field of organic chemistry. The study reports on the palladium-catalyzed Suzuki-Miyaura cross-coupling of N-acylcarbazoles and N-acylindoles with arylboronic acids, achieving highly selective N?C(O) bond cleavage. The key finding is that the ground-state destabilization of the amide bond stems from Nlp to Ar conjugation, which enables reactivity similar to N-acylsulfonamide and N-acylcarbamate activation in simple anilides. This activation concept allows for the catalytic generation of acylmetals by a combined steric and electronic destabilization.
10.1016/0008-6215(88)80166-6
This research aims to synthesize modified oligosaccharides for use as substrates in studies related to glycosidase and glycosyltransferases. The authors adopted a method described by Nakabayashi et al. to synthesize glycopyrano-oxazolines, which alleviates difficulties encountered in previous methods. They synthesized 2-methyl-(3,6-di-O-acetyl-1,2,4-trideoxy-4-fluoro-a-D-glucopyrano)-[2,1-d]-2-oxazoline (6), a previously unknown compound, and demonstrated its utility for introducing a 2-acetamido-2-deoxy-?-D-glucopyranosyl group with a fluorine atom at C-4 by synthesizing benzyl 2-acetamido-6-O-(2-acetamido-2,4-dideoxy-4-fluoro-?-D-glucopyranosyl)-2-deoxy-a-D-galactopyranoside (8). Key chemicals used include benzyl 2-acetamido-3,6-di-O-benzyl-2,4-dideoxy-4-fluoro-a-D-glucopyranoside (1) as the starting material, diethylaminosulfur trifluoride for fluorination, palladium-on-charcoal for hydrogenolysis, acetic anhydride for acetylation, and trimethylsilyl trifluoromethanesulfonate for the formation of oxazoline 6. The synthesis process involves multiple steps, including fluorination, hydrogenolysis, acetylation, and glycosylation, with the final product 8 confirmed by NMR spectroscopy. The study concludes that the adopted method is effective for synthesizing the desired modified oligosaccharides.
10.1021/ol048313c
The study presents a novel one-pot method for the synthesis of enantiomerically enriched α-arylated cycloalkanones through the sequential Cu-catalyzed reduction and Pd-catalyzed arylation of silyl enol ethers. The process involves the use of enantiomerically enriched diphenylsilyl enol ethers, prepared from Cu-catalyzed asymmetric conjugate reduction, which are then utilized in the Pd-catalyzed arylation of various aryl bromides. This approach provides an efficient route to α-arylated cycloalkanones with excellent levels of enantiomeric and diastereomeric purity, overcoming the limitations of direct ketone arylation. Key chemicals used include copper (Cu) and palladium (Pd) catalysts, silyl enol ethers, aryl bromides, and various phosphine ligands. The purpose of these chemicals is to facilitate the selective formation of the desired arylation products with high stereochemical control, which are valuable in the synthesis of natural products and pharmaceuticals.
10.1021/jm00398a027
The research focuses on the synthesis and evaluation of polyoxin L analogues containing α-amino fatty acids with saturated fatty acid-like side chains for their potential as anticandidal agents. The purpose of the study was to develop synthetic polyoxins that could be designed to have increased affinity for a peptide transport system and increased stability against intracellular degradation in Candida albicans. The researchers synthesized analogues of polyoxin L using benzyloxycarbonyl-protected α-amino fatty acid p-nitrophenyl esters and uracil polyoxin C, yielding diastereomeric dipeptidyl polyoxin L analogues containing α-aminooctanoic acid, α-aminododecanoic acid, or α-aminohexadecanoic acid. These analogues were tested for their ability to inhibit chitin synthetase from Candida albicans, compete for peptide transport, and resist hydrolysis by cell extracts. The conclusions drawn from the study were that synthetic polyoxin L analogues with alkane-like side chains were effective substrates for the dipeptide transport system in C. albicans, efficient chitin synthetase inhibitors, and in some cases, stable to candidal cell extracts. However, the most potent analogue, compound 4, showed a minimum inhibitory concentration of 40-80 pg/mL, which may not be sufficient for clinical applications. The research involved a series of chemical syntheses, including the use of palladium black, formic acid, and various amino acids and their derivatives, such as α-aminooctanoic acid, α-aminododecanoic acid, and α-aminohexadecanoic acid, among others.