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1.
The viability of the iridium complex of pybox as chiral catalyst in allylic substitutions and the enantioselective synthesis of branched products was studied. Among several chiral ligands evaluated, the iridium complex of pybox having a phenyl group catalyzed the reaction with high activity to form the branched amines with good enantioselectivities when hydroxylamine, amine, and aniline were employed as a nucleophile. The allylic substitution with oximes proceeded smoothly to give the branched oxime ethers with good enantioselectivities. [reaction: see text] 相似文献
2.
Long Li Feng Han Xin Nie Yubiao Hong Sergei Ivlev Eric Meggers 《Angewandte Chemie (International ed. in English)》2020,59(30):12392-12395
A strategy for expanding the utility of chiral pyridine‐2,6‐bis(oxazoline) (pybox) ligands for asymmetric transition metal catalysis is introduced by adding a bidentate ligand to modulate the electronic properties and asymmetric induction. Specifically, a ruthenium(II) pybox fragment is combined with a cyclometalated N‐heterocyclic carbene (NHC) ligand to generate catalysts for enantioselective transition metal nitrenoid chemistry, including ring contraction to chiral 2H‐azirines (up to 97 % ee with 2000 TON) and enantioselective C(sp3)?H aminations (up to 97 % ee with 50 TON). 相似文献
3.
Sandeep K. Ginotra 《Tetrahedron》2006,62(15):3573-3581
Copper complexes of chiral tridentate pybox ligands synthesized using a modified procedure have been studied as catalysts for the enantioselective allylic oxidation of olefins. A variety of olefins have been used in this reaction. Using 5 mol% of a Cu(II) complex of the tridentate pybox ligand, phenylhydrazine, and tert-butyl perbenzoate as oxidant in acetone, optically active allylic benzoates were obtained up to 94% ee in few hours. It was also observed that the use of molecular sieves in the reaction did not alter the enantioselectivity. Temperature was found to be very crucial in rate of the enantioselective allylic oxidation of olefins. Using EPR spectra, it has been shown that the Cu(II) species is reduced to Cu(I) by phenylhydrazine and phenylhydrazone, but the reduction with the former is faster in comparison to the latter. It was concluded that the rate enhancement was not specific to the presence of phenylhydrazine or phenylhydrazone, but both were equally responsible provided acetone was used as a solvent. 相似文献
4.
Bidentate and tetradentate ligands containing the oxazoline unit have been successful in a range of asymmetric transformations.[1~3] Chiral tridentate ligands may form a deeper chiral concave pocket around the metal center, and have been less extensively used in asymmetric catalysis than their bidentate or tetradentate analogues. Nishiyama's tridentate "pybox"ligand, in which a pyridine ring links two chiral oxazoline moieties, has been successfully used in various asymmetric reactions. 相似文献
5.
Copper(I) and copper(II) complexes of two bis(oxazolinyl)pyridines were immobilized on silica via electrostatic interactions. The catalytic activity of the immobilized catalysts in the direct addition of terminal alkynes to imines leading to propargylamines was investigated under a variety of reaction conditions. The performance of the immobilized catalysts compares very well with their homogeneous equivalents. When used in toluene, the catalysts could be recycled a number of times and maintained activity. This study is the first such report of the immobilization on silica in this manner of any bis(oxazolinyl)pyridine (pybox) complex. 相似文献
6.
7.
Enantioselective syn-selective scandium-catalyzed ene reactions 总被引:2,自引:0,他引:2
An enantio- and diastereoselective carbonyl-ene reaction catalyzed by chiral scandium pyridyl bis(oxazoline) (pybox) complexes has been developed. Uniformly high enantiomeric excesses and good yields were observed. Use of trisubstituted olefins generated the syn product in high enantio- and diastereoselectivity. 相似文献
8.
Marie-Ève Thérien Audrey-Anne Guilbault Claude Y. Legault 《Tetrahedron: Asymmetry》2013,24(19):1193-1197
A new family of iodooxazoline catalysts, derived from widely available chiral ketones (menthone and camphor), was developed to promote the iodine(III)-mediated α-tosyloxylation of ketone derivatives. The reaction conditions to achieve the direct formation of the oxazoline moieties from the corresponding aminoalcohols and an aldehyde were explored and optimized. These catalysts were tested for the α-tosyloxylation of propiophenone and led to new information on the stereoinduction process. The results demonstrate that modulation of the steric hindrance around the iodane center is critical to obtain good activity. Additionally, from the selectivities observed, a preliminary predictive model is proposed. 相似文献
9.
[reaction: see text] An enantio- and diastereoselective Sakurai-Hosomi reaction, catalyzed by chiral scandium pyridyl-bis(oxazoline) (pybox) complexes, has been developed. Both alkyl- and aryl-substituted allylsilanes are effective coupling partners with N-phenylglyoxamide. Applications of this reaction to the asymmetric syntheses of N-Boc D-alloisoleucine and D-isoleucine are described. 相似文献
10.
[reaction: see text] The viability of hydroxylamines as nucleophiles in transition-metal-catalyzed allylic substitutions was examined. We have found that the oxygen atom of hydroxylamines having an N-electron-withdrawing substituent (also known as hydroxamic acids) acts as a reactive nucleophile. The palladium-catalyzed O-allylic substitution of hydroxylamines with allylic carbonate afforded the linear hydroxylamines. The selective formation of the branched hydroxylamines was observed in iridium-catalyzed reaction. Regio- and enantioselective allylic substitution of the unsymmetrical phosphates with hydroxylamines was studied by using the iridium complex of chiral pybox ligand. The aqueous-medium reaction with hydroxylamines proceeded smoothly in the presence of Ba(OH)(2).H(2)O to give the branched products with good enantioselectivities. 相似文献
11.
A highly enantioselective, quinone Diels-Alder reaction catalyzed by chiral samarium and gadolinium pyridyl-bis(oxazoline) (pybox) complexes has been developed. The reaction scope has been extended to include three quinones and five dienes, all of which exclusively provide the expected endo product in excellent yields and enantioselectivities. 相似文献
12.
Monolithic macroporous Pt/CeO2/Al2O3 catalysts were prepared using concentrated emulsions synthesis route, and the obtained samples
were characterized with SEM, TG, TEM, XRD and TPR techniques. These monolithic catalysts were applied to water gas shift (WGS)
reaction in reformed gases. The SEM and TEM results indicated that the monoliths possessed macroporosity, and that the platinum particles
homogeneously dispersed on the supports with the particle size in the range of 1−2 nm. The reducibility of the catalysts was characterized
by TPR method, and it was shown that the monolithic PtOx/CeO2/Al2O3 exhibited the similar reducibility property to that of the particle
PtOx/CeO2 reported in literatures. The CO conversion over the monolithic catalysts is higher than that over micro-reactor catalysts for WGS
reaction in the reformed gases conditions, indicating that the monolithic macroporous catalysts is a potential new route for miniaturization of
WGS reactor. 相似文献
13.
Dr. Cheng Sheng Dr. Zheng Ling Dr. Junzhe Xiao Kai Yang Prof. Dr. Fang Xie Prof. Dr. Shengming Ma Prof. Dr. Wanbin Zhang 《Angewandte Chemie (International ed. in English)》2023,62(31):e202305680
The skeletons of chiral tetrasubstituted allenes bearing a vicinal all-carbon quaternary stereocenter are of importance but still challenging to synthesize. Herein, we report enantio- and diastereoselective γ-additions of 1-alkynyl ketimines with dual-copper-catalysis under mild conditions, affording chiral tetrasubstituted α-amino allenoates bearing a vicinal all-carbon quaternary stereocenter in high yields (up to 99 % yield) with excellent enantioselectivities (up to 99 % ee) and diastereoselectivities (up to >20 : 1 dr). Importantly, the stereodivergent synthesis of the products was realized by the asymmetric γ-addition reaction and the Grignard reagent promoted epimerization. Moreover, the dual-copper-catalyzed γ-addition reactions were smoothly applied to a gram-scale reaction and adopted to introduce chiral tetrasubstituted allenyl moieties into bioactive molecules. Mechanistic experiments and density functional theory (DFT) calculations demonstrated that the asymmetric γ-addition reactions were catalyzed by double chiral copper catalysts. 相似文献
14.
Fan Fu 《Tetrahedron letters》2006,47(25):4267-4269
A chiral indium(III) complex prepared from indium triflate and a pybox ligand has been developed to give good yields and enantioselectivities (up to 92% ee) in the addition of (1-methoxy-2-methyl-propenyloxy)-trimethylsilane to various aromatic and aliphatic aldehydes via the Mukaiyama aldol reaction. 相似文献
15.
The oxygen atom of oximes acts as a reactive nucleophile in the iridium-catalyzed allylic substitution of unsymmetrical substrates to give the branched oxime ethers. Among several chiral ligands evaluated, the iridium complex of pybox ligand having phenyl group catalyzed the allylic substitution of phosphates with high activity to form the branched oxime ethers with good enantioselectivities. 相似文献
16.
Direct Asymmetric Dearomatization of 2‐Naphthols by Scandium‐Catalyzed Electrophilic Amination 下载免费PDF全文
Jiang Nan Prof. Dr. Jingjing Liu Huayu Zheng Zhijun Zuo Prof. Dr. Lei Hou Prof. Dr. Huaiming Hu Prof. Dr. Yaoyu Wang Prof. Dr. Xinjun Luan 《Angewandte Chemie (International ed. in English)》2015,54(8):2356-2360
Catalytic asymmetric aminative dearomatization of 1‐substituted 2‐naphthols was successfully implemented with electrophilic azodicarboxylates under the catalysis of chiral ScIII/pybox complexes. This intermolecular reaction represents a hitherto unknown enantioselective C? N bond‐forming process through direct dearomatization of phenolic compounds to generate chiral nitrogen‐containing quaternary carbon stereocenters. 相似文献
17.
Dr. Kathrin Junge Konstanze Möller Bianca Wendt Shoubhik Das Dr. Dirk Gördes Prof. Dr. Kerstin Thurow Prof. Dr. Matthias Beller 《化学:亚洲杂志》2012,7(2):314-320
The combination of ZnEt2 and chiral pyridinebisoxazoline (pybox) or pyridinebisimidazoline (pybim) ligands catalyzed the asymmetric hydrosilylation of aryl, alkyl, cyclic, heterocyclic, and aliphatic ketones. Under mild conditions, high yields and good enantioselectivities were achieved. ESI measurements allowed for the characterization of the active catalyst. 相似文献
18.
Immobilized catalysts have attracted chemists’ attention for long time because of convenient recycling, which is very important for some special catalyst even immobilizations accompanying the decrease of catalytic activity and selectivity. Our group focused on the developing chiral catalysts with camphor framework to catalyze various asymmetric reactions for long time. For easily recycling the unique chiral catalysts, a series of polymer catalysts with chiral camphor unit were synthesized by RAFT polymerization. Herein, the performance of the synthesized polymer chiral catalysts was reported by catalyzing asymmetric Henry reaction. After optimizing the reaction conditions, the synthesized chiral polymer catalyst provides a good yield and enantioselectivity to the reaction of p-nitrobenzaldehyde and nitromethane. In the meantime, the recycles and reused properties of synthesized polymer catalysts were examination by the model asymmetric Henry reaction. The catalyzed activities and enantioselectivities did not show obviously decrease until recycling five times. 相似文献
19.
Using the cinchonidine-derived phase-transfer catalyst developed by Park and Jew as a lead structure, we have prepared novel chiral ammonium salts and investigated their efficacy for the preparation of β-hydroxy α-amino acids via asymmetric aldol reactions. The modifications were performed at C3 of the cinchonidine nucleus and include dimers as well as catalysts possessing electron-deficient alkyne and alkene moieties. Some of the new catalysts yielded improvements relative to the Park-Jew catalyst in the aldol reaction. 相似文献