683-60-3Relevant articles and documents
Unprecedented formation of cis- and trans-di[(3-chloropropyl) isopropoxysilyl]-bridged double-decker octaphenylsilsesquioxanes
Ervithayasuporn, Vuthichai,Sodkhomkhum, Rapheepraew,Teerawatananond, Thapong,Phurat, Chuttree,Phinyocheep, Pranee,Somsook, Ekasith,Osotchan, Tanakorn
, p. 3292 - 3296 (2013)
Silsesquioxane formation competing with the deprotonation of alcohol solvents in the presence of a strong base to form alkoxides is reported for the first time. Evidently, sodium isopropoxide is formed during the synthesis of the sodium salt of a double-decker octaphenylsilsesquioxane tetrasilanolate in 2-propanol as the solvent, which leads to the formation of unexpected cis- and trans-di[(3-chloropropyl)isopropoxysilyl]-bridged double-decker octaphenylsilsesquioxanes after in situ coupling with 3- chloropropyltrichlorosilane. The desired products were characterized by 1H NMR, 13C NMR, and 29Si NMR spectroscopy; ESI-MS; and single-crystal X-ray diffraction. During the synthesis of the sodium salt of double-decker octaphenylsilsesquioxane tetrasilanolate in 2-propanol, sodium isopropoxide is formed, which leads to the formation of unexpected cis- and trans-di[(3-chloropropyl)isopropoxysilyl]-bridged double-decker octaphenylsilsesquioxanes after in situ coupling with 3- chloropropyltrichlorosilane. Copyright
Synthesis and application of 1-benzyl-4-methyl-5-alkoxy-1, 2, 3, 6-tetrahydropyridine derivative
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Paragraph 0119-0122, (2021/04/14)
The invention relates to the field of synthesis of drug intermediates, in particular to the field of synthesis of key intermediates for preparing anti-rheumatoid arthritis drug tofacitinib, and specifically relates to a 1-benzyl-4-methyl-5-alkoxy-1, 2, 3, 6-tetrahydropyridine compound, a synthetic method thereof, and an application of the 1-benzyl-4-methyl-5-alkoxy 1, 2, 3, 6-tetrahydropyridine compound in preparation of a key intermediate cis-1-benzyl-3-methylamino-4-methyl piperidine of tofacitinib.
Catalytic Regioselective Olefin Hydroarylation(alkenylation) by Sequential Carbonickelation-Hydride Transfer
Liu, Chen-Fei,Luo, Xiaohua,Wang, Hongyu,Koh, Ming Joo
supporting information, p. 9498 - 9506 (2021/07/19)
Alkene hydrocarbofunctionalization represents one of the most important classes of chemical transformations, but related branched-selective examples with unactivated olefins are scarce. Here, we report that catalytic amounts of a dimeric Ni(I) complex and an exogenous alkoxide base promote Markovnikov-selective hydroarylation(alkenylation) of unactivated and activated olefins using organo bromides or triflates derived from widely available phenols and ketones. Products bearing aryl- and alkenyl-substituted tertiary and quaternary centers could be isolated in up to 95% yield and >99:1 regioisomeric ratios. Contrary to previous dual-catalytic methods that rely on metal-hydride atom transfer (MHAT) to the olefin prior to carbofunctionalization with a cocatalyst, our mechanistic evidence points toward a nonradical reaction pathway that begins with site-selective carbonickelation across the C═C bond followed by hydride transfer using alkoxide as the hydride source. Utility of the single-catalyst protocol is highlighted through the synthesis of medicinally relevant scaffolds.
Rhodium-Catalyzed meta-Selective C?H Carboxylation Reaction of 1,1-Diarylethylenes via Hydrorhodation-Rhodium Migration
Caner, Joaquim,Iwasawa, Nobuharu,Saito, Takanobu,Toriumi, Naoyuki
supporting information, p. 23349 - 23356 (2021/09/18)
A meta-selective C?H carboxylation reaction of 1,1-diarylethylene derivatives with CO2 by using a rhodium catalyst with NaOiPr as a stoichiometric reductant has been achieved. Together with hydrogenation of the ethylene moiety, a carboxyl group was introduced to the meta-position of the aryl ring with high selectivity over the ortho-positions. Experimental and computational mechanistic studies indicate that this carboxylation reaction proceeds via hydrorhodation on the ethylene moiety, followed by 1,4-rhodium migration and successive 1,2-rhodium migration on the aryl ring. The use of a bulky phosphine ligand seems to be the key to this unusual aryl-to-aryl 1,2-rhodium shift.
NHC-CDI Betaine Adducts and Their Cationic Derivatives as Catalyst Precursors for Dichloromethane Valorization
Sánchez-Roa, David,Mosquera, Marta E. G.,Cámpora, Juan
, p. 16725 - 16735 (2021/11/18)
Zwitterionic adducts of N-heterocyclic carbene and carbodiimide (NHC-CDI) are an emerging class of organic compounds with promising properties for applications in various fields. Herein, we report the use of the ICyCDI(p-Tol) betaine adduct (1a) and its cationic derivatives2aand3aas catalyst precursors for the dichloromethane valorization via transformation into high added value products CH2Z2(Z = OR, SR or NR2). This process implies selective chloride substitution of dichloromethane by a range of nucleophiles Na+Z-(preformed or generatedin situfrom HZ and an inorganic base) to yield formaldehyde-derived acetals, dithioacetals, or aminals with full selectivity. The reactions are conducted in a multigram-scale under very mild conditions, using dichloromethane both as a reagent and solvent, and very low catalyst loading (0.01 mol %). The CH2Z2derivatives were isolated in quantitative yields after filtration and evaporation, which facilitates recycling the dichloromethane excess. Mechanistic studies for the synthesis of methylal CH2(OMe)2rule out organocatalysis as being responsible for the CH2transfer, and a phase-transfer catalysis mechanism is proposed instead. Furthermore, we observed that1aand2areact with NaOMe to form unusual isoureate ethers, which are the actual phase-transfer catalysts, with a strong preference for sodium over other alkali metal nucleophiles.
BORON CONTAINING COMPOUNDS AND THEIR USES
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Paragraph 0296; 0297, (2020/03/29)
The present disclosure contemplates novel boron-containing compounds and their uses as active agents that exhibit pesticidal activity such as antimicrobial, insecticidal, arachnicidal, and/or anti parasitic activity. An agrochemical composition containing such a compound and its use in, animal health, agriculture, or horticulture is also contemplated. A method for promoting plant performance and/or controlling, reducing, preventing, ameliorating, or inhibiting microbes, insects, arachnids, and/or parasites on or in an animal, a plant, a plant part, plant propagation material, and/or harvested fruits or vegetables is also contemplated.
Asymmetric Transfer Hydrogenation with a Bifunctional Iron(II) Hydride: Experiment Meets Computation
De Luca, Lorena,Passera, Alessandro,Mezzetti, Antonio
supporting information, (2019/02/14)
Hydride cis-β-[FeH(CNCEt3)(1)]BF4 (5) (1 is a chiral N2P2 macrocycle) is the catalytically active species in the asymmetric transfer hydrogenation of ketones formed upon reaction of [Fe(CNCEt3)2(1)](BF4)2 (3) with base. Stoichiometric reactions show that hydride 5 is formed by H-elimination from the 2-propoxo complex [Fe(OiPr)(CNCEt3)(1)]BF4 (8a) and inserts the C=O bond of acetophenone to give the diastereoisomeric alcoholato complexes [Fe(OCH(Me)Ph)(CNCEt3)(1)]BF4 (10R and 10S). Complexes 5, 8a, and 10 were characterized by NMR spectroscopy, and their structures were calculated by DFT. The DFT study supports a bifunctional mechanism with the alkoxo complexes 8a and 10 as resting species. The stereochemical model reproduces the high enantioselectivity with acetophenone, which results from the combination of the rigid macrocyclic scaffold with the bulky, yet conformationally flexible isonitrile.
Surface properties of ceria synthesised using Triton-X based reverse microemulsions
Paschalidou, Polyxeni,Theocharis, Charis R.
, p. 7025 - 7031 (2019/03/14)
The effect of the tail length of Triton-X surfactants on the surface properties of ceria prepared by means of reversed micelles and Ce(OiPr)4 has been systematically studied. Generally, solids with increased surface areas (up to 136 m2 g-1) were synthesised. It was shown that the tail length strongly affects the surface characteristics. Further studies were carried out using UV-Vis, ATR-FTIR, XRD and TGA/DSC studies of the precursor gels as well as N2-isothermal adsorption BET, XRD, FT-IR, UV-Vis diffuse reflectance and SEM investigations of the final solids samples. An interaction mechanism between the ceria precursor molecules and the polar tail of the reversed Triton X micelles and the formation of ceria (CeO2) particles in the aqueous nucleus of the reversed microemulsions is proposed.
ISOXAZOLE DERIVATIVES FOR USE IN THE TREATMENT OF PULMONARY DISEASES AND DISORDERS
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Paragraph 0497-0500, (2017/03/21)
The present disclosure features disclosed method of treating disorders such as COPD, bronchitis and/or asthma using disclosed compounds, optionally together with one or more additional active agents. Contemplated methods include administrating orally or by inhalation to a patient one or more disclosed compounds.
Highly Enantioselective Hydrogenation of Amides via Dynamic Kinetic Resolution Under Low Pressure and Room Temperature
Rasu, Loorthuraja,John, Jeremy M.,Stephenson, Elanna,Endean, Riley,Kalapugama, Suneth,Clément, Roxanne,Bergens, Steven H.
supporting information, p. 3065 - 3071 (2017/03/11)
High-throughput screening and lab-scale optimization were combined to develop the catalytic system trans-RuCl2((S,S)-skewphos)((R,R)-dpen), 2-PrONa, and 2-PrOH. This system hydrogenates functionalized α-phenoxy and related amides at room temperature under 4 atm H2 pressure to give chiral alcohols with up to 99% yield and in greater than 99% enantiomeric excess via dynamic kinetic resolution.
