Refernces
10.1002/adsc.202100296
The research focuses on the semi-rational engineering of toluene dioxygenase (TDO) from Pseudomonas putida F1 to enhance its capability for the oxyfunctionalization of bicyclic aromatic compounds. The study involved generating single and double mutant libraries targeting 27 different positions at the active site and entrance channel of TDO. A total of 176 variants were created and tested with substrates such as naphthalene, 1,2,3,4-tetrahydroquinoline, and 2-phenylpyridine. Key mutations at positions M220, A223, and F366 significantly influenced product formation, chemo-, regio-, and enantioselectivity. The engineered TDO variants demonstrated the ability to convert bulkier substrates with unprecedented conversions, leading to the production of valuable chiral synthons like (+)-(R)-1,2,3,4-tetrahydroquinoline-4-ol and (+)-(1S,2R)-3-(pyridin-2-yl)cyclohexa-3,5-diene-1,2-diol with high yields and enantiomeric excess. The experiments utilized site-directed mutagenesis, biotransformations in recombinant E. coli strains, and analyses including HPLC-DAD, HPLC-ESI-MS, chiral HPLC-DAD, and NMR spectroscopy for product identification, quantification, and characterization.
10.1002/zaac.201500625
The study investigates the catalytic activity of two palladium(II) complexes, [PdCl(ppy)(IMes)] (4) and [PdCl(ppy){(CN)2IMes}] (6), in the Mizoroki-Heck reaction, a crucial cross-coupling reaction in the synthesis of pharmaceuticals and natural products. These complexes feature different N-heterocyclic carbene (NHC) ligands, IMes and (CN)2IMes, with the latter having a higher π-acceptor strength. The purpose of the study is to evaluate how the π-acceptor strength of the NHC ligands affects the catalytic performance of the complexes. The chemicals used include palladium(II) chloride, 2-phenylpyridine, 1,3-bis(mesityl)imidazol-2-ylidene (IMes), 4,5-dicyano-1,3-bis(mesityl)imidazol-2-ylidene ((CN)2IMes), and aryl halides, which serve as substrates in the Mizoroki-Heck reaction. The study aims to develop more effective precatalysts for this reaction by understanding the influence of the NHC ligands' electronic properties on the reaction's efficiency.
10.1021/ja00385a038
The research involves two separate studies. The first study focuses on the total synthesis of the 16-membered ring macrolide antibiotic tylonolide hemiacetal. Key chemicals used in this research include chiral bicyclo[2.2.1]heptenol, which was elaborated into the C(3)-C(9) and C(11)-C(17) fragments through a series of complex organic reactions involving reagents such as benzyl chloride, boron trifluoride etherate, lithium aluminum hydride, and m-chloroperbenzoic acid. The synthesis also utilized various solvents like methylcyclohexane and tetrahydrofuran, and involved steps like benzoylation, olefin inversion, and allylic oxidation to ultimately achieve the coupling of the fragments and the formation of the 16-membered macrolide ring. The second study investigates the photochemical formation of tetracarbonyl(4,4’-dialkyl-2,2’-bipyridine)metal from hexacarbonylmetal using rapid-scan Fourier transform infrared spectroscopy. Chemicals such as W(CO)6, 4,4’-(n-C19H39)2-2,2’-bpy, and 2-phenylpyridine were used to observe the formation of monodentate intermediates in the reaction. The study provides direct infrared spectral evidence for the formation of these intermediates, highlighting the role of CO and the bipyridine ligands in the photochemical process.
10.1021/om4007032
The research, investigates the synthesis, properties, and potential applications of cyclometalated iridium(III) complexes incorporating azadipyrromethene ligands. The purpose of this study is to combine the visible excitability of azadipyrromethenes with the triplet-state photoproperties of iridium(III) complexes, aiming to create new materials with desirable optical and electrochemical properties for applications in areas such as light-emitting diodes (OLEDs), metal ion sensors, and biological tags. The researchers used base-assisted transmetalation from boron to synthesize a series of iridium(III) complexes with various cyclometalating ligands, such as 2-phenylpyridine (ppy), p-tolylpyridine (tpy), and 2-phenylbenzothiazole (bt), and azadipyrromethene ligands like LaBr2. The resulting complexes were characterized by various techniques, including X-ray crystallography, cyclic voltammetry, and density functional theory (DFT) calculations. The key findings include the preservation of the common four-aryl geometry of azadipyrromethenes in the six-coordinate iridium(III) complexes, the dominance of azadipyrromethene absorption bands in the optical spectra, and the identification of the azadipyrromethene as the site of one-electron reduction. The study concludes that these new complexes exhibit electroactive properties with reversible reductions and oxidations, and their optical properties are mainly governed by the azadipyrromethene ligand. The results suggest that the electrooptical properties of azadipyrromethene ligands could be extended to other metal complexes and materials, opening up new possibilities for the development of functional materials.
10.1021/acs.inorgchem.7b01307
The research focuses on the synthesis and characterization of a series of tris-heteroleptic iridium complexes based on cyclometalated ligands with different cores, specifically [Ir(C^N1)(C^N2)(acac)] complexes, where C^N1 and C^N2 are 2-phenylpyridine (ppy), 2-(2,4-difluorophenyl)pyridine (dFppy), 1-phenylpyrazole (ppz), and 1-(2,4-difluorophenyl)pyrazole (dFppz). The purpose of this study was to explore how the structure of these complexes, particularly the positioning of substituents, affects their photophysical and electrochemical properties. The researchers found that while the overall architecture of the complex primarily dictates static properties such as absorption and emission spectra and redox potentials, dynamic properties like excited-state lifetime and radiative and nonradiative rate constants are sensitive to the specific positioning of the substituents.