- Organic luminescent material containing 6-silicon-based substituted isoquinoline ligand
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Disclosed is an organic light-emitting material containing a 6silicon-based substituted isoquinoline ligand. The organic light-emitting material is a metal complex containing a 6silicon-based substituted isoquinoline ligand, and can be used as a light-emitting material in a light-emitting layer of an organic light-emitting device. These novel complexes can provide more red and saturated emissions,and can also exhibit significantly improved lifetime and high efficiency excellent device performance. An electroluminescent device and a compound formulation comprising the metal complex are also disclosed.
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Paragraph 0159; 0163-0165
(2020/11/22)
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- Metal complex containing three different ligands
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A metal complex containing three different ligands is disclosed. The metal complex contains three different ligands, and can be used as a luminescent material in a luminescent layer of an organic electroluminescent device. The novel complexes not only can achieve the device performance expected to be regulated or improved by regulating substituent groups, but also can achieve the effect of effectively controlling the rise of the evaporation temperature. An electroluminescent device and a compound formulation comprising the metal complex are also disclosed.
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Paragraph 0142; 0146-0148
(2020/11/22)
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- Palladium-catalyzed 2-pyridylmethyl-directed β-C(sp3)–H activation and cyclization of aliphatic amides with gem-dibromoolefins: A rapid access to γ-lactams
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The direct Pd-catalyzed β-C(sp3)–H activation and cyclization of aliphatic amides bearing a removable 2-pyridylmethyl directing group with gem-dibromoolefins is described for the first time to construct a variety of γ-lactams. The resulting products with Z- and E-configurations can be easily separated and purified after the reaction, demonstrating the effectiveness and applicability of the method herein developed.
- Zhou, Danni,Wang, Chunxia,Li, Mingliang,Long, Zheng,Lan, Jingbo
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supporting information
p. 191 - 193
(2017/11/17)
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- Palladium-Catalyzed C(sp3)-H Oxygenation via Electrochemical Oxidation
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Palladium-catalyzed C-H activation/C-O bond-forming reactions have emerged as attractive tools for organic synthesis. Typically, these reactions require strong chemical oxidants, which convert organopalladium(II) intermediates into the PdIII or PdIV oxidation state to promote otherwise challenging C-O reductive elimination. However, previously reported oxidants possess significant disadvantages, including poor atom economy, high cost, and the formation of undesired byproducts. To overcome these issues, we report an electrochemical strategy that takes advantage of anodic oxidation of PdII to induce selective C-O reductive elimination with a variety of oxyanion coupling partners.
- Yang, Qi-Liang,Li, Yi-Qian,Ma, Cong,Fang, Ping,Zhang, Xiu-Jie,Mei, Tian-Sheng
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supporting information
p. 3293 - 3298
(2017/03/11)
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- Auxiliary-Directed C(sp3)?H Arylation by Synergistic Photoredox and Palladium Catalysis
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Herein we describe the auxiliary-directed arylation of unactivated C(sp3)?H bonds with aryldiazonium salts, which proceeds under synergistic photoredox and palladium catalysis. The site-selective arylation of aliphatic amides with α-quaternary centres is achieved with high selectivity for β-methyl C(sp3)?H bonds. This operationally simple method is compatible with carbocyclic amides, a range of aryldiazonium salts and proceeds at ambient conditions.
- Czyz, Milena L.,Lupton, David W.,Polyzos, Anastasios
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supporting information
p. 14450 - 14453
(2017/10/07)
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- Nickel-catalyzed directed sulfenylation of sp2 and sp3 C-H bonds
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Directed sulfenylation of both sp2 and sp3 C-H bonds was achieved through nickel catalyzed directed C-S bond formation, giving the desired product in good to excellent yield (up to 90%). Other metal cations, including Cu, Fe, Pd, Rh, Ru and Co, gave almost no reaction under identical conditions, which highlighted the unique reactivity of this Ni system.
- Ye, Xiaohan,Petersen, Jeffrey L.,Shi, Xiaodong
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supporting information
p. 7863 - 7866
(2015/05/13)
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- Nickel-catalyzed site-selective alkylation of unactivated C(sp 3)-H bonds
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The direct alkylation of unactivated sp3 C-H bonds of aliphatic amides was achieved via nickel catalysis with the assist of a bidentate directing group. The reaction favors the C-H bonds of methyl groups over the methylene C-H bonds and tolerates various functional groups. Moreover, this reaction shows a predominant preference for sp3 C-H bonds of methyl groups via a five-membered ring intermediate over the sp2 C-H bonds of arenes in the cyclometalation step.
- Wu, Xuesong,Zhao, Yan,Ge, Haibo
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supporting information
p. 1789 - 1792
(2014/03/21)
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- Copper-catalyzed site-selective intramolecular amidation of unactivated C(sp3)-H bonds
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The intramolecular dehydrogenative amidation of aliphatic amides, directed by a bidentate ligand, was developed using a copper-catalyzed sp3 C-H bond functionalization process. The reaction favors predominantly the C-H bonds of β-methyl groups over the unactivated methylene C-H bonds. Moreover, a preference for activating sp3 C-H bonds of β-methyl groups, via a five-membered ring intermediate, over the aromatic sp2 C-H bonds was also observed in the cyclometalation step. Additionally, sp3 C-H bonds of unactivated secondary sp3 C-H bonds could be functionalized by favoring the ring carbon atoms over the linear carbon atoms. Getting ahead on tams: The intramolecular dehydrogenative amidation of aliphatic amides, directed by a bidentate ligand, was developed using a copper-catalyzed sp 3 C-H bond functionalization process to deliver β-lactams. The reaction favors the C-H bonds of β-methyl groups over the unactivated methylene C-H bonds, as well as aromatic C(sp2)-H bonds and unactivated secondary C(sp3)-H bonds of rings.
- Wu, Xuesong,Zhao, Yan,Zhang, Guangwu,Ge, Haibo
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supporting information
p. 3706 - 3710
(2014/04/17)
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- CATALYTICS ASYMMETRIC ACTIVATION OF UNACTIVATED C-H BONDS, AND COMPOUNDS RELATED THERETO
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One aspect of the present invention is directed in part to catalytic and stereoselective functionalization of unactivated C-H bonds of simple organic substrates. The compounds and methods provided herein allow one to control the stereochemistry in a C-H activation step, activate substrates containing α-hydrogens next to the directing group, and remove a directing group under mild conditions. One aspect of the present invention relates to a transition-metal-catalyzed method for selective and asymmetric oxidation of carbons located in a β- or γ-position relative to an auxiliary. Another aspect of the invention relates to the enantiomerically-enriched substrates and the enantiomerically-enriched products formed via said method. In certain embodiments, oxazoline and oxazinone directing groups are used. In addition, the Boc protecting group has been identified as a directing group which does not necessitate removal.
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Page/Page column 76-77; 89-90
(2010/10/20)
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- Process for synthesis of tertiary carboxylic acids and the esters thereof
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The present invention provides a process for synthesizing tertiary carboxylic acids or the esters thereof having one or two more carbon atoms than the raw material has, comprising reacting in a strong acid (e.g., sulfuric acid, sulfuric acid-phosphoric acid, hydrogen fluoride, fluorosulfuric acid, boron trifluoride.water complex and trifluoromethanesulfonic acid) a raw material compound (i.e., olefin, alcohol, diene, diol or saturated hydrocarbon) with carbon monoxide in the presence of a specific metal carbonyl catalyst (i.e., platinum carbonyl catalyst, palladium carbonyl catalyst and gold dicarbonyl catalyst). The metal carbonyl catalyst is formed by reacting in a strong acid at least one specific metal compounds (e.g., platinum compound such as platinum (II, IV) oxide, platinum (II, IV) hydroxide, a platinum powder, etc.; palladium compound such as palladium (II, III, IV) oxide, palladium (II) hydroxide, palladium (II) sulfate, palladium (II) carboxylate, a palladium powder, etc.; and gold compound such as gold (I, III) oxide, gold (I, III) hydroxide, a gold powder, etc.) with carbon monoxide.
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- Novel application of a solid super acid, sulfated zirconia, as a catalyst for Koch carbonylation reaction
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A solid superacid, sulfated zirconia, worked well in the Koch reaction. Under optimized conditions, tertiary alcohols were selectively transformed to the corresponding carboxylic acids (34-72%), while primary alcohols were transformed to the corresponding ethers (58-72%).
- Mori, Hajime,Wada, Aya,Xu, Qiang,Souma, Yoshie
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p. 136 - 137
(2007/10/03)
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- Palladium(I) Carbonyl Cation-Catalyzed Carbonylation of Olefins and Alcohols in Concentrated Sulfuric Acid
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A new palladium catalyst was found to exhibit high catalytic activity for carbonylation of olefins and alcohols. cyclo-Bis(μ-carbonyl)dipalladium(I) cation (1) with bridging CO ligands is formed by reductive carbonylation of palladium sulfate, PdSO4, in concentrated H2SO4. When an olefin or alcohol is added, complex 1 changes to a new complex (2) with terminal CO ligands, and tertiary carboxylic acids are obtained in high yields at room temperature and atmospheric pressure of CO. IR and 13C NMR studies suggest that complex 2 may be tentatively formulated to be [Pd2(CO)2]2+, in which the terminal CO ligands are chemically equivalent. Complex 1 is a catalyst precursor, and complex 2 functions as an active species for the carbonylation of olefins and alcohols. The catalytic behavior of the palladium carbonyl catalyst supports the recently proposed reaction mechanism involving an olefin-metal-CO complex as an intermediate for the catalytic carbonylation of olefins and alcohols in strongly acidic solution.
- Xu, Qiang,Souma, Yoshie,Umezawa, Junya,Tanaka, Mutsuo,Nakatani, Hisako
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p. 6306 - 6311
(2007/10/03)
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- A New Gold Catalyst: Formation of Gold(I) Carbonyl, [Au(CO)n]+ (n = 1, 2), in Sulfuric Acid and Its Application to Carbonylation of Olefins
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A new gold catalyst, [Au(CO)n]+ (n = 1, 2), was synthesized by using a facile method from commercial gold(III) oxide, Au2O3, in concentrated H2SO4, which exhibits high catalytic activity for carbonylation of olefins. The gold monocarbonyl [Au(CO)]+ (1) and dicarbonyl [Au(CO)2]+ (2) cations coexist in H2SO4 solution, the former of which is much more stable than the latter. Both of the carbonyls show IR spectra of vCO (2194, 2208 cm-1) higher than that of free CO (2143 cm-1), indicating nonclassical (σ-only) gold-CO bonding. The gold carbonyl complexes coexisting in the concd H2SO4 solution exhibit a single resonance in the 13C NMR spectrum at 171 ppm at ambient temperature and pressure, reflecting rapid CO exchange between 1 (164 ppm) and 2 (175 ppm). The nonclassical gold(I) carbonyl solution worked as an excellent catalyst, with which olefins reacted with CO to give tert-carboxylic acids in good yields at room temperature and atmospheric pressure. The gold(I) dicarbonyl cation 2 was found to function as an active species for the carbonylation. An olefin-gold(I)-carbonyl complex was proposed as a possible intermediate in the metal carbonyl-catalyzed carbonylation in the strongly acidic medium.
- Xu, Qiang,Imamura, Yuki,Fujiwara, Masahiro,Souma, Yoshie
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p. 1594 - 1598
(2007/10/03)
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- Pyridylthio-acylanilide herbicides
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Novel herbicidally active pyridylthio-acylanilides of the formula STR1 in which R1, R2 and R3, independently of one another, represent hydrogen, halogen, cyano or trifluoromethyl or alkyl, alkoxy and alkylthio having 1 to 4 carbon atoms in each case, R4 represents halogen, methyl or methoxy, n represents a number 0, 1 or 2, z represents the group (Ia) STR2 or the group (Ib) STR3 where X represents oxygen, sulphur, an N--R10 or N--O--R11 group, or X and Rg tpgether represent the STR4 radical, and the other radicals can have various meanings. Intermediates of the formulae STR5 are also new.
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- Hydroxyacetonitrile diphosphonic acid, a process for its production, and its use
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Hydroxyacetonitrile diphosphonic acid corresponding to the following general formula STR1 in which M represents H or a cation of a base, and salts thereof; to a process for their preparation comprising reacting 3-R1 -3-oxo-1-aminopropane-1,1-diphosphonic acids corresponding to the following general formula STR2 in which R1 is a tertiary substituted alkyl group, an optionally substituted cycloalkyl group or an optionally substituted aryl or heteroaryl radical, with nitrous acid, the secondary product R1 -COOH and unreacted starting material are separated off from the reaction mixture and the hydroxyacetonitrile diphosphonic acid is obtained in the form of a salt by addition of a base; and to the use of the above compounds as complexing agents and as thresholders.
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- HIGHLY SELECTIVE SYNTHESIS OF ACYCLIC TERT-ALIPHATIC CARBOXYLIC ACIDS FROM ACYCLIC TERT-ALCOHOLS USING SULFURIC ACID SUPERSATURATED WITH CARBON MONOXIDE
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The selective carboxylation of acyclic tert-aliphatic alcohols was successfully performed to produce the corresponding acyclic tert-aliphatic carboxylic acids in significantly high yields using concentrated sufuric acid supersaturated with carbon monoxide.
- Takahashi, Yukio,Yoneda, Norihiko
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p. 1945 - 1954
(2007/10/02)
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- Synthesis, Properties and Structure of New 1,1-Diphosphonic Acids
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The synthesis of 3-tert-alkyl-3-oxo-1-aminopropane-1,1-diphosphonic acids and of 3-tert-alkyl-3-oxo-prop-1-ene-1,1-diphosphonic acids as two new groups of metal complexing agents and their chemical properties are described.Evidence is given for their suggested structures.In addition, the first known example of a diphosphonic acid with a cyano group attached to the geminal carbon atom was prepared from 3-oxo-1-aminoalkane-1,1-diphosphonic acids and 3-tert-alkyl-3-oxo-1-hydroxypropane-1,1-diphosphonic acids from 3-oxo-1-aminopropane-1,1-diphosphonic acids. - Keywords: 3-tert-Alkyl-3-oxo-1-aminopropane-1,1-diphosphonic Acids, 3-tert-Alkyl-3-oxo-1-hydroxypropane-1,1-diphosphonic Acids, 3-tert-Alkyl-3-oxo-prop-1-ene-1,1-diphosphonic Acids, Diphosphonocyanohydrin, Preparation
- Blum, Helmut
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- SYNTHESIS OF ESTERS FROM 1-HEXANOL AND ETHYL FORMATE UNDER CONDITIONS OF SULFURIC ACID CATALYSIS
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The ethoxycarbonylation of 1-hexanol in one stage with concentrated sulfuric acid as catalyst and ethyl formate as acylating and esterifying agent was investigated.The products are mainly ethyl 2,2-dimethylpentanoate, 2-methyl-2-ethylbutyrate, and 2-ethylpentanoate and the corresponding acids.The content of the esters and acids with a quaternary carbon atom at position 2 in the reaction mixture increased with increase in the molar ratio of sulfuric acid to alcohol, with decrease in the molar ratio of ethyl formate to sulfuric acid, with increase in the rate of addition of the alcohol to the sulfuric acid, and with increase in the reaction temperature.
- Ordyan, M. B.,Stepanyan, A. A.,Pirozhkov, S. D.,Manukyan, Sh. M.,Grigoryan, V. S.,Lapidus, A. L.
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p. 1429 - 1432
(2007/10/02)
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- STERIC EFFECTS IN SYSNTHESIS - STERIC LIMITS TO THE ALKYLATION OF NITRILES AND CARBOXYLIC ACIDS
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The steric limits to the alkylation of aliphatic nitriles and carboxylic acids have been investigated in some detail.For the experimental conditions considered (ionization by i-Pr2NLi in THF followed by alkylation with RI/THF/HMPA) the most hindered nitriles R-CN and carboxylic acids R-CO2H have the same secondary alkyl group R=t-BuiPrCH-, but different tertiary, i.e.R=t-BuiPrEtC- or i-Pr3C- for RCN and R=Et2MeC for RCO2H.A comparison of the relative merits of alkylation of esters, carboxylic acids, and nitriles is considered.
- MacPhee, John-Anthony,Dubois, Jacques-Emile
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p. 775 - 778
(2007/10/02)
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- ACTION DES DIALKYLCUPRATES DE LITHIUM SUR LES ALDEHYDES α,β-ETHYLENIQUES
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Nearly exclusive 1-4 addition products are obtained by action of lithium dialkylcuprates with α,β-ethylenic aldehydes.Non polar solvents and low temperatures favor this reaction.Only α,β-ethylenic aldehydes having a trisubstituted double bond give a relatively important proportion of 1-2 addition product.
- Chuit, C.,Foulon, J. P.,Normant, J. F.
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p. 2305 - 2310
(2007/10/02)
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