24740-01-0Relevant academic research and scientific papers
Optimized Scalable Synthesis of Chiral Iridium Pyridyl-Phosphinite (Pyridophos) Catalysts
Müller, Marc-André,Gani?, Adnan,H?rmann, Esther,Kaiser, Stefan,Maywald, Matthias,Roseblade, Stephen J.,Schrems, Marcus G.,Schumacher, Andreas,Woodmansee, David,Pfaltz, Andreas
, (2020/12/01)
Iridium catalysts with chiral P,N ligands have greatly enhanced the scope of asymmetric olefin hydrogenation because they do not require a coordinating group near the C=C bond like Rh and Ru catalysts. Pyridophos ligands, possessing a conformationally restricted annulated pyridine framework linked to a phosphinite group, proved to be particularly effective, inducing high enantioselectivities in the hydrogenation of a remarkably broad range of substrates. Here we report the development of an efficient scalable synthesis for the two most versatile Ir-pyridophos catalysts, derived from 2-phenyl-8-hydroxy-5,6,7,8-tetrahydroquinoline or the analogue with a five-membered carbocyclic ring, respectively, by modification and optimization of the original synthetic route. The optimized route renders both catalysts readily accessible in multi-gram quantities in analytically pure form in overall yields of 26–37 %, starting from acetophenone and cyclopentanone or cyclohexanone, respectively. A major advantage of the new synthesis is the efficient and practical kinetic resolution of the late-stage pyridyl alcohol intermediates with commercial immobilized Candida antarctica lipase B, giving access to both enantiomers of these catalysts as essentially enantiopure compounds. The catalysts are obtained as crystalline solids, which are air-stable and can be stored for years at ?20 °C without notable decomposition.
Photophysical properties and OLED performance of light-emitting platinum(ii) complexes
Kourkoulos, Dimitrios,Karakus, Cüneyt,Hertel, Dirk,Alle, Ronald,Schmeding, Sebastian,Hummel, Johanna,Risch, Nikolaus,Holder, Elisabeth,Meerholz, Klaus
supporting information, p. 13612 - 13621 (2013/09/23)
The synthesis, photophysical properties and application as emitters in solution-processed multi-layer organic light-emitting diodes (OLEDs) of a series of blue-green to red light-emitting phosphorescent platinum(ii) complexes are reported. These complexes consist of phenylisoquinoline, substituted phenylpyridines or tetrahydroquinolines as C^N cyclometalating ligands and dipivaloylmethane as an ancillary ligand. Depending on both the structure of the C^N cyclometalating ligands and the dopant concentration in the matrix, these platinum(ii) complexes exhibit different aggregation tendencies. This property affects the photoluminescence spectra of the investigated compounds and colour-stability of the fabricated OLEDs. Using the blue-green to yellow-green emitting complexes, the best results were obtained with the 2-(4- trifluoromethylphenyl)-5,6,7,8-tetrahydroquinoline based platinum(ii) complex. A maximum luminous efficiency of 4.88 cd A-1 and a power efficiency of 4.65 lm W-1, respectively, were achieved. Employing the red emitting phenylisoquinoline based complex as an emitter, colour-stable and efficient (4.71 cd A-1, 5.12 lm W-1) devices were obtained.
Microwave-mediated facile synthesis of steroid-like 1,5-diketones from Mannich salts
Rao, H. Surya Prakash,Poonguzhali,Senthilkumar
, p. 937 - 942 (2008/09/17)
A facile synthesis of some diketones that fit into a steroid motif was achieved from Mannich salts and cyclic ketones under microwave irradiation. Copyright Taylor & Francis Group, LLC.
Iridium catalysts with bicyclic pyridine-phosphinite ligands: Asymmetric hydrogenation of olefins and furan derivatives
Kaiser, Stefan,Smidt, Sebastian P.,Pfaltz, Andreas
, p. 5194 - 5197 (2007/10/03)
(Chemical Equation Presented) Superior bicyclics: Iridium catalysts as 1 derived from pyridine-phosphinite ligands considerably extend the scope of asymmetric hydrogenation. In addition to various unfunctionalized and functionalized olefins, furans, and benzofurans, for which no catalysts were known before, are also hydrogenated with high enantioselectivity (see scheme).
Generation of β-keto radicals from cyclopropanols catalyzed by AgNO3
Chiba, Shunsuke,Cao, Zhengyan,El Bialy, Serry Atta Atta,Narasaka, Koichi
, p. 18 - 19 (2007/10/03)
Various β-keto radicals are generated from cyclopropanols by treatment with a catalytic amount of AgNO3 and (NH4) 2S2O8 as a reoxidant in the presence of pyridine. Thus, generated β-keto radicals react with alkenes to yield addition products. Copyright
Novel domino products from the reaction of phenyl vinyl ketone and its derivatives with cyclic ketones
Surya Prakash Rao,Jeyalakshmi,Senthilkumar
, p. 2189 - 2199 (2007/10/03)
Reaction of phenyl vinyl ketone with cyclopentanone under thermal conditions resulted in novel domino products, 1,5,9-triketones along with the expected 1,5-diketones. The 1,5,9-triketones were formed via a Michael-Michael-rearrangement pathway. On the other hand, reaction under basic conditions furnished a spiro[4.5]decanone, formed by domino pathways involving Michael-Michael-aldol condensation reactions. Microwave mediated reductive amination-cyclization of the 1,5,9-triketone furnished the perhydrocyclopenta[ij]quinolizine derivative.
Hydrogen-bonding in cyclic 2-(3-oxo-3-phenylpropyl)-substituted 1,3-diketones: 17O-NMR spectra and X-ray structure determination
Zhuo, Jin-Cong,Schenk, Kurt
, p. 1276 - 1283 (2007/10/03)
Structures of cyclic 2-(3-oxo-3-phenylpropyl)-substituted 1,3-diketones 4a-c were determined by 17O-NMR spectroscopy and X-ray crystallography. In CDCl3 solution, compounds 4a-c form an eight-membered-ring with intramolecular H-bondi
Efficient Preparation of Substituted 5,6,7,8-Tetrahydroquinolines and Octahydroacridine Derivatives
Sielemann, Dirk,Keuper, Ralf,Risch, Nikolaus
, p. 487 - 491 (2007/10/03)
The reaction of the enamine 4 with different β-amino ketone hydrochlorides 3a-e affords the diketones 5a-e which can be cyclized to the corresponding mono- and disubstituted tetrahydroquinolines 6a-e. Furthermore the preparation of the octahydroacridines 8f and 8g by using a straightforward multi step sequence is described.
Surface-mediated Solid Phase Reaction. Part 6. Mukaiyama-Michael Addition of Silyl Ethers to Alkyl Vinyl Ketones on the Surface of Alumina: a Simple and Convenient Method for the Synthesis of 1,5-Diketones
Ranu, Brindaban C.,Saha, Manika,Bhar, Sanjay
, p. 2197 - 2200 (2007/10/02)
Michael addition of silyl enol and dienol ethers to alkyl vinyl ketones occurs in high yields through a simple solvent-free reaction on the surface of anhydrous zinc chloride-impregnated alumina to give 1,5-diketones.
