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111.
Dr. Alexey V. Polukeev 《欧洲无机化学杂志》2023,26(31):e202300351
Synthesis, characterization and catalytic activity of cyclometalated iridium complexes with a bidentate POC ligand is presented. Metalation of POC-H (di-tert-butyl(phenoxy)phosphane) with [Ir(COD)Cl]2 proceeded rapidly at room temperature and afforded mixture of (POC)(POC-H)IrHCl ( 1 a ) and (POC)(COD)IrHCl ( 1 b ), from which complexes (POC)(L)IrHCl where L=PPh3 ( 1 c ), bipyridine ( 1 d ) and [2,2′-bipyridine]-6,6′-diol ( 1 e ) were prepared through ligand exchange. The compounds were tested in acceptorless dehydrogenation of 1-phenylethanol and transfer dehydrogenation of ethanol in a context of comparison with pincer counterparts (POCOP)IrHCl and (PCN)IrHCl. An attempt to prepare a dihydride complex from 1 e led to dimeric complex [(POC)(bipy-diol−)IrH]2 ( 3 ) that could explain the low activity of 1 e . DFT studies provided insight into POC-H vs POCOP-H metalation mechanism. 相似文献
112.
Alexander A. Bredikhin Zemfira A. Bredikhina Alexey V. Kurenkov Dmitry B. Krivolapov 《Tetrahedron: Asymmetry》2017,28(3):442-446
Racemic 3-(4-indolyloxy)-1,2-propanediol 2 has been effectively resolved into (S)- and (R)-enantiomers by a preferential crystallization procedure. Non-racemic (S)-2 was converted into (S)-4-(2,3-epoxypropoxy)-1H-indole (S)-4 via a Mitsunobu reaction and then into (S)-pindolol (S)-1. The crystalline (S)-1 was studied by single crystal X-ray diffraction. A large number of symmetry independent molecules (Z′ = 6) led to a weakening of the system of strong intermolecular hydrogen bonds, which combined with a loose packing (PI = 64.6%), may be the cause of the abnormally low melting point of (S)-1 as compared with rac-1. 相似文献
113.
Marina Tarasenko Nikolay Duderin Tatyana Sharonova Sergey Baykov Anton Shetnev Alexey V. Smirnov 《Tetrahedron letters》2017,58(37):3672-3677
An efficient and mild one-pot protocol has been developed for the synthesis of 1,2,4-oxadiazoles via the reaction of amidoximes with dicarboxylic acid anhydrides in a NaOH/DMSO medium. The method allows the synthesis of diversely substituted carboxylic acids bearing the 1,2,4-oxadiazole motif, – a popular building block for pharmaceutical research, in moderate to excellent yields. The reaction scope includes aromatic and heteroaromatic amidoximes as well as five-, six- and seven-membered anhydrides. The advantages of this procedure are proven gram-scalability and the use of inexpensive starting materials, which from a process chemistry point of view are essential for future industrial applications. 相似文献
114.
115.
Osipov SN Golubev AS Sewald N Michel T Kolomiets AF Fokin AV Burger K 《The Journal of organic chemistry》1996,61(21):7521-7528
A new method for the preparation of alpha-chlorodifluoromethyl-, alpha-bromodifluoromethyl-, and alpha-difluoromethyl-substituted alpha-hydroxy and alpha-amino acid esters 11, 19-21 is described. The key step of the synthesis is the regioselective alkylation of ketones 5, 7-9 and imines 16-18 with C-nucleophiles. The ketones 7-9 are readily available from 3,3,3-trifluorolactate 1 by a five-step procedure. Subsequent removal of the protecting groups from 19-21 provides the corresponding free amino acids 25, 26, 28. 相似文献
116.
Irina Yu. Bagryanskaya Yuri V. Gatilov Alexander Yu. Makarov Alexander M. Maksimov Alexey O. Miller Makhmut M. Shakirov Andrey V. Zibarev 《Heteroatom Chemistry》1999,10(2):113-124
Despite some limitations, the 1:1 condensation of n‐RC6H4‐N=S=N‐SiMe3 (n = 2, 3, 4; R = CH3, OCH3, F, Cl, CF3) with SCl2, followed by intramolecular electrophilic ortho‐cyclization, was found to be a general synthetic approach to the corresponding 5‐R, 6‐R, and 7‐R–substituted 1,3,2,4‐benzodithiadiazines, formally antiaromatic 12π‐electron compounds. For precursors with n = 3, the high regioselectivity of the cyclization resulted in exclusive (R = OCH3, F) or predominant (R = CH3, Cl) formation of 6‐R isomers; the ratio of the major 6‐R isomer to the minor 8‐R one was found to be 72:28 (R = CH3) or 78:22 (R = Cl). The preferred direction of cyclization is consistent with thermodynamics of the corresponding intermediate σ‐complexes as well as factors of kinetic control for an orbital‐controlled El‐Nu reaction. According to the X‐ray diffraction data, the molecules of 5‐CF3 (15) and 6‐F (12) derivatives are nearly planar, while the molecules of 5‐OCH3 (7) and 6‐CH3 (4) derivatives are bent along the S1 … N4 line by ∼11° (7) or 7° (4). An attempt to adopt CsF‐induced intramolecular nucleophilic ortho‐cyclization of ArF‐S‐N=S=N‐SiMe3 into polyfluorinated 1,3,2,4‐benzodithiadiazines for polyfluoropyridine derivatives resulted in formation of polyfluorinated aminopyridines. Data obtained are consistent with a previously suggested scheme of sulfur–nitrogen chain shortening during cyclization. Mild acid hydrolysis of the title compounds was shown to be a convenient synthetic route to substituted 2,2′‐diaminodiphenyl disulfides (including polyfluorinated ones) via the corresponding 2‐aminobenzenethiols. © 1999 John Wiley & Sons, Inc. Heteroatom Chem 10: 113–124, 1999 相似文献
117.
Yaroslav V. Kudryavtsev Arkady D. Litmanovich Alexey G. Makeev Sergey V. Bogomolov 《Macromolecular theory and simulations》1999,8(2):161-171
A theory describing slow macromolecular reaction and interdiffusion in a compatible polymer blend is extended to consider H‐bonding. The known treatments of H‐bonding influence on the free energy of mixing and chains' mobilities are combined to calculate mutual diffusion coefficients in the framework of linear non‐equilibrium thermodynamics. Numerical calculations are performed for a blend of two random copolymers AC and BC to reveal the effect of H‐bonding (between A and B, B and B units) on the interdiffusion profiles. Then, the transformation of A units into B ones is included and the reaction‐diffusion equations are solved with the parameters corresponding to the blend of poly(tert‐butyl acrylate‐co‐styrene) with poly‐(acrylic acid‐co‐styrene) in which the thermal decomposition of tert‐butyl acrylate units takes place. The numerical calculations show that this system is suitable for the experimental verification of theoretical predictions concerning the interplay between macromolecular reaction and interdiffusion in polymer blends. 相似文献
118.
Dmitrii Semenok Alexey Kletskov Evgenij Dikusar Vladimir Potkin Oleg Lukin 《Tetrahedron letters》2018,59(4):372-374
A library of 4′-chloro- and 4′-fluorosulfonyl-substituted chalcones was prepared via the aldol-type condensation reactions of 4-acetylbenzene-1-sulfonyl halides with various aromatic aldehydes, either in absolute ethanol or glacial acetic acid, in the presence of dry HCl. This represents the first examples of chalcone sulfonyl halides in which the phenone ring bears one of these functional groups. The reactivity of the chalcone sulfonyl halides were strongly dependent on the styrene ring substituents; sulfonyl chlorides reacted with most nucleophiles (e.g. amines, alcohols), while sulfonyl fluorides reacted only with charged nucleophiles (e.g. phenolates). 相似文献
119.
120.
Mikhail N. Feofanov Boris A. Lozhkin Maksim V. Anokhin Alexey D. Averin Irina P. Beletskaya 《Mendeleev Communications》2018,28(4):429-430
Magnesium iodide-catalyzed addition of electron-rich (het)arenes to ethyl glyoxylate proceeds at room temperature with high chemoselectivity to afford ethyl 2-(het)aryl- 2-hydroxyacetates in yields up to 95%. 相似文献