- Photoredox/nickel-catalyzed hydroacylation of ethylene with aromatic acids
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We report a general, practical and scalable hydroacylation reaction of ethylene with aromatic carboxylic acids with the synergistic combination of nickel and photoredox catalysis. Under ambient temperature and pressure, feedstock chemicals such as ethylene can be converted into high-value-added aromatic ketones in moderate to good yields (up to 92%) with reaction time of 2-6 hours.
- Chen, Shuai,He, Hengchi,Li, Weipeng,Xie, Jin,Zhang, Lili,Zhu, Chengjian
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supporting information
p. 9064 - 9067
(2021/09/15)
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- Iridium Complexes as Efficient Catalysts for Construction of α-Substituted Ketones via Hydrogen Borrowing of Alcohols in Water
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Ketones are of great importance in synthesis, biology, and pharmaceuticals. This paper reports an iridium complexes-catalyzed cross-coupling of alcohols via hydrogen borrowing, affording a series of α-alkylated ketones in high yield (86 %–95 %) and chemoselectivities (>99 : 1). This methodology has the advantages of low catalyst loading (0.1 mol%) and environmentally benign water as the solvent. Studies have shown the amount of base has a great impact on chemoselectivities. Meanwhile, deuteration experiments show water plays an important role in accelerating the reduction of the unsaturated ketones intermediates. Remarkably, a gram-scale experiment demonstrates this methodology of iridium-catalyzed cross-coupling of alcohols has potential application in the practical synthesis of α-alkylated ketones.
- Luo, Nianhua,Zhong, Yuhong,Wen, Huiling,Shui, Hongling,Luo, Renshi
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p. 1355 - 1364
(2021/03/03)
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- Synthetic method of 3 '-methyl propiophenone
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The invention belongs to the field of organic synthesis, and discloses a synthetic method of 3 '-methyl propiophenone. The method comprises the following steps: taking m-tolualdehyde as a raw material, carrying out affinity addition reaction with an ethyl Grignard reagent to obtain 3 '-methyl phenylpropanol; and then using oxygen as an oxidizing agent, using a composite catalyst composed of nitroxide free radicals, inorganic bromide and nitrite, and performing catalytic oxidation on 3 '-methyl phenylpropanol to generate 3'-methyl propiophenone. The adopted composite catalyst is good in stability and selectivity, high in yield (up to 90% or above), reusable, safe and environment-friendly in the whole process and suitable for industrial production.
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Paragraph 0036; 0038-0039; 0041-0042; 0044
(2020/07/21)
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- Cobalt-Catalyzed Migrational Isomerization of Styrenes
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An efficient cobalt-catalyzed migrational isomerization of styrenes was developed using the thiazoline iminopyridine (TIP) ligand. This reaction is operationally simple and atom-economical using readily available starting materials to access trisubstituted alkenes. Even when using a 0.1 mol % catalyst loading, the reaction could be conducted in neat and completed in 1 h with excellent conversion and high E stereoselectivity.
- Zhao, Jiajin,Cheng, Biao,Chen, Chenhui,Lu, Zhan
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supporting information
p. 837 - 841
(2020/01/31)
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- Novel benzene-based carbamates for ache/bche inhibition: Synthesis and ligand/structure-oriented sar study
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A series of new benzene-based derivatives was designed, synthesized and comprehensively characterized. All of the tested compounds were evaluated for their in vitro ability to potentially inhibit the acetyl-and butyrylcholinesterase enzymes. The selectivity index of individual molecules to cholinesterases was also determined. Generally, the inhibitory potency was stronger against butyryl-compared to acetylcholinesterase; however, some of the compounds showed a promising inhibition of both enzymes. In fact, two compounds (23, benzyl ethyl(1-oxo-1-phenylpropan-2-yl)carbamate and 28, benzyl (1-(3-chlorophenyl)-1-oxopropan-2-yl) (methyl)carbamate) had a very high selectivity index, while the second one (28) reached the lowest inhibitory concentration IC50 value, which corresponds quite well with galanthamine. Moreover, comparative receptor-independent and receptor-dependent structure–activity studies were conducted to explain the observed variations in inhibiting the potential of the investigated carbamate series. The principal objective of the ligand-based study was to comparatively analyze the molecular surface to gain insight into the electronic and/or steric factors that govern the ability to inhibit enzyme activities. The spatial distribution of potentially important steric and electrostatic factors was determined using the probability-guided pharmacophore mapping procedure, which is based on the iterative variable elimination method. Additionally, planar and spatial maps of the host–target interactions were created for all of the active compounds and compared with the drug molecules using the docking methodology.
- Bak, Andrzej,Kozik, Violetta,Kozakiewicz, Dariusz,Gajcy, Kamila,Strub, Daniel Jan,Swietlicka, Aleksandra,Stepankova, Sarka,Imramovsky, Ales,Polanski, Jaroslaw,Smolinski, Adam,Jampilek, Josef
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- Method for generating ketone through rearranging diazo compounds under catalysis condition of ferrous sulfate heptahydrate
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The invention provides a method for generating ketone through rearranging diazo compounds to remove one molecule of nitrogen gas and one molecule of carbon dioxide under a certain condition. The method comprises the following steps of adding diazo compound 2-diazo-1-phenylbutane-1,3-diketone and iron sulfate heptahydrate into a reaction container; then adding methylbenzene; performing stirring reaction for 12 hours at 100 DEG C; after the reaction is completed, performing filtering by a kieselguhr sand core funnel; after rotary drying, performing column separation to obtain pure products. Thepreparation method is simple and convenient; the cost is low; the conditions are mild; the yield can reach 80 percent or higher. The method belongs to a novel method for generating ketone. A positiveresearch is provided for the application of the compound.
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Paragraph 0018; 0019; 0020; 0021; 0023; 0027; 0028; 0029
(2018/09/08)
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- Enantioselective Hydrogen Atom Transfer: Discovery of Catalytic Promiscuity in Flavin-Dependent 'Ene'-Reductases
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Flavin has long been known to function as a single electron reductant in biological settings, but this reactivity has rarely been observed with flavoproteins used in organic synthesis. Here we describe the discovery of an enantioselective radical dehalogenation pathway for α-bromoesters using flavin-dependent 'ene'-reductases. Mechanistic experiments support the role of flavin hydroquinone as a single electron reductant, flavin semiquinone as the hydrogen atom source, and the enzyme as the source of chirality.
- Sandoval, Braddock A.,Meichan, Andrew J.,Hyster, Todd K.
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supporting information
p. 11313 - 11316
(2017/08/30)
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- General, Simple, and Chemoselective Catalysts for the Isomerization of Allylic Alcohols: The Importance of the Halide Ligand
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Remarkably simple IrIIIcatalysts enable the isomerization of primary and sec-allylic alcohols under very mild reaction conditions. X-ray absorption spectroscopy (XAS) and mass spectrometry (MS) studies indicate that the catalysts, with the general formula [Cp*IrIII], require a halide ligand for catalytic activity, but no additives or additional ligands are needed.
- Erbing, Elis,Vázquez-Romero, Ana,Bermejo Gómez, Antonio,Platero-Prats, Ana E.,Carson, Fabian,Zou, Xiaodong,Tolstoy, P?ivi,Martín-Matute, Belén
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supporting information
p. 15659 - 15663
(2016/10/25)
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- The genetic incorporation of thirteen novel non-canonical amino acids
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Thirteen novel non-canonical amino acids were synthesized and tested for suppression of an amber codon using a mutant pyrrolysyl-tRNA synthetase-tRNAPylCUA pair. Suppression was observed with varied efficiencies. One non-canonical amino acid in particular contains an azide that can be applied for site-selective protein labeling. The Royal Society of Chemistry 2014.
- Tuley, Alfred,Wang, Yane-Shih,Fang, Xinqiang,Kurra, Yadagiri,Rezenom, Yohannes H.,Liu, Wenshe R.
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supporting information
p. 2673 - 2675
(2014/03/21)
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- Rhodium-catalyzed ketone methylation using methanol under mild conditions: Formation of α-branched products
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The rhodium-catalyzed methylation of ketones has been accomplished using methanol as the methylating agent and the hydrogen-borrowing method. The sequence is notable for the relatively low temperatures that are required and for the ability of the reaction system to form α-branched products with ease. Doubly alkylated ketones can be prepared from methyl ketones and two different alcohols by using a sequential one-pot iridium- and rhodium-catalyzed process. Uniquely effective for making branched alkyl products from ketones (see scheme): The scope of the presented reaction includes aromatic and aliphatic ketones and consecutive one-pot double alkylation reactions to provide a convenient route to branched ketones from simple methyl ketones. A brief study into the mechanism of the reaction has given evidence for an aldol-based reaction pathway.
- Chan, Louis K. M.,Poole, Darren L.,Shen, Di,Healy, Mark P.,Donohoe, Timothy J.
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supporting information
p. 761 - 765
(2014/01/23)
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- Rhodium-catalyzed ortho acylation of aromatic carboxylic acids
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New directions: The carboxylic acid functional group directs the ortho acylation of benzoic acids with carboxylic anhydrides in the presence of a rhodium catalyst (see scheme; cod=cyclo-1,5-octadiene). The acylation at the ortho position is complementary to the meta selectivity of Friedel-Crafts reactions. The resulting products can undergo protodecarboxylation to deliver an aryl ketone. Copyright
- Mamone, Patrizia,Danoun, Gregory,Goossen, Lukas J.
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p. 6704 - 6708
(2013/07/26)
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- Atom efficient Friedel-Crafts acylation of toluene with propionic anhydride over solid mesoporous superacid UDCaT-5
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Friedel-Crafts acylation is ubiquitous in industry and is typically carried out by using more than stoichiometric quantities of homogeneous catalysts. This creates pollution. In this work, acylation of toluene was studied in liquid phase with propionic anhydride with a variety of solid superacids to produce 4′-methylpropiophenone (4′-MPP). The solid superacids were modified versions of zirconia, namely, UDCaT-4, UDCaT-5 and UDCaT-6 developed in our laboratory; amongst which UDCaT-5 was the most active, selective and robust catalyst. The effects of various reaction parameters on the rate of reaction and selectivity were investigated to deduce the intrinsic kinetics of the reaction. The reaction is free from any external mass transfer as well as intraparticle diffusion limitations and is intrinsically kinetically controlled. The acylation conditions were: temperature 180 °C, toluene to propionic anhydride molar ratio 5:1, catalyst loading 0.06 g cm-3, speed of agitation 1000 rpm, under autogenous pressure in a stainless steel autoclave reactor. Propionic acid generated in situ also reacts sequentially with toluene to give 4′-MPP. A conversion of 62% of priopionic anyhydride is obtained after 3 h, with 100% mono-acylated product containing 67% 4′-MPP. Water is the only co-product of the overall reaction. A suitable kinetic model was developed. The reactions were carried out without using any solvent in order to make the process cleaner and greener.
- Yadav, Ganapati D.,Kamble, Shashikant B.
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experimental part
p. 265 - 274
(2012/08/28)
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- MONOAM1NE REUPTAKE INHIBITORS
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The invention provides bupropion analogue compounds capable of inhibiting the reuptake of one or more monoamines. The compounds may selectively bind to one or more monoamine transporters, including those for dopamine, norepinephrine,and serotonin. Such compounds may be used to treat conditions that are responsive to inhibition of the reuptake of monoamines, including addiction, depression, and obesity
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Page/Page column 65
(2010/11/04)
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- N, N′-dioxide-Cu(OTf)2 complex catalyzed highly enantioselective amination reaction of N-acetyl enamide
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The N,N′-dioxide-Cu(OTf)2 complexes were applied in the asymmetric amination reaction of N-acetyl enamides with dialkyl azodicarboxylate, giving the corresponding products in good yields with high enantioselectivities (up to 91% ee). Precursors of vicinal diamine were readily obtained with excellent diastereoselectivities (>95:5) by NaBH4 reduction.
- Chang, Lu,Kuang, Yulong,Qin, Bo,Zhou, Xin,Liu, Xiaohua,Lin, Lili,Feng, Xiaoming
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supporting information; scheme or table
p. 2214 - 2217
(2010/08/06)
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- CYCLOBUTENEDIONE DERIVATIVES
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The present invention relates to compounds of the formula (I): to pharmaceutically acceptable salts therefore and to pharmaceutically acceptable solvates of said compounds and salts, wherein the substituents are defined herein; to compositions containing such compounds; and to the uses of such compounds in the treatment of various diseases, particularly inflammatory conditions.
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Page/Page column 73
(2010/12/17)
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- Synthesis and biological evaluation of bupropion analogues as potential pharmacotherapies for cocaine addiction
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A series of bupropion (1a) analogues (1b-1ff) were synthesized, and their in vitro and in vivo pharmacological properties evaluated with the goal of developing a 1a analogue that had better properties for treating addictions. Their in vitro pharmacological properties were examined by [3H] dopamine ([3H]DA), [3H]serotonin ([3H]5HT), and [3H]norepinephrine ([3H]NE) uptake inhibition studies, and by binding studies at the dopamine, serotonin, and norepinephrine transporters using [125I]RTI-55 in cloned transporters. Several analogues showed increased [3H]DAuptake inhibition with reduced or little change in [3H]5HT and [3H]NE uptake inhibition relative to bupropion. Thirty-five analogues were evaluated in a 1 h locomotor activity observation test and 32 in an 8 h locomotor activity observation test and compared to the locomotor activity of cocaine. Twenty-four analogues were evaluated for generalization to cocaine drug discrimination after i.p. administration, and twelve analogues were tested in a time course cocaine discrimination study using oral administration. 2-(N-Cyclopropylamino)-3- chloropropiophenone (1x) had the most favorable in vitro efficacy and in vivo pharmacological profile for an indirect dopamine agonist pharmacotherapy for treating cocaine, methamphetamine, nicotine, and other drugs of abuse addiction. 2009 American Chemical Society.
- Carroll, F. Ivy,Blough, Bruce E.,Abraham, Philip,Mills, Andrew C.,Holleman, J. Ashley,Wolckenhauer, Scott A.,Decker, Ann M.,Landavazo, Antonio,McElroy, K. Timothy,Navarro, Hernán A.,Gatch, Michael B.,Forster, Michael J.
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supporting information; experimental part
p. 6768 - 6781
(2010/04/06)
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- Chloroindate(III) ionic liquids: Recyclable media for Friedel-Crafts acylation reactions
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Chloroindate(III) ionic liquids are versatile reaction media for Friedel-Crafts acylation reactions; the system is catalytic and totally recyclable, using an aqueous workup, with no leaching of the indium into the product phase. The Royal Society of Chemistry 2005.
- Earle, Martyn J.,Hakala, Ullastiina,Hardacre, Christopher,Karkkainen, Johanna,McAuley, Barry J.,Rooney, David W.,Seddon, Kenneth R.,Thompson, Julian M.,Waehaelae, Kristina
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p. 903 - 905
(2007/10/03)
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- Amine derivatives
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The present invention relates to amine derivatives represented by formula (1) or salts thereof. R3represents C1-C3 alkyl, hydroxylated C1-C5 alkyl, C1-C5 acyl; C2-C5 alkenyl, or a halogen atom; and k, l, and m are each an integer of 1 to 4.) Exhibiting excellent antifungal effect, these compounds are highly useful as antifungal agents, antifungal compositions, drugs, etc.
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- Photochemistry of substituted propiophenones: An interesting α-and aryl substituents effect on their photobehaviour
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Photochemistry of different α-substituted and phenyl-substituted propiophenones in methanol is investigated with a view to delineate the substituent effect with a special reference tu their rearrangement to α-arylpropanoic acids, an important class of nonsteroidal antiinflammatory agents. The results thus obtained bringsforth an important element of their reactivityprofile i.e. the α-chloro-substituent in combination with nuclear alkyl substituents (para>meta) favours 1,2-arylmigration leading to the synthetically useful reaction for α-arylpro panoic acids.
- Sonawane, Harikisan R.,Bellur, Nanjundiah S.,Nazeruddin
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p. 11281 - 11294
(2007/10/02)
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- Synthesis and activity of 2-methyl-3-aminopropiophenones as centrally acting muscle relaxants
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Some novel 2-methyl-3-aminopropiophenones were synthesized and their centrally acting muscle relaxant activities were,evaluated for an inhibitory effect on the flexor reflex in rats. The structure-activity relationships are discussed. In this series 2-methyl-3-pyrrolidino-1-(4-trifluoromethylphenyl)-propan-1-one (28) showed significant centrally acting muscle relaxant activity. In addition, the activities of each enantiomer (28-(S) and (R)) were studied along with their acute toxicities. Compound 28-(R) was found to exhibit more potent activity and weaker acute toxicity than 28-(S). Accordingly, compound 28-(R) (NK433) is under development as a novel centrally acting muscle relaxant.
- Shiozawa,Narita,Izumi,Kurashige,Sakitama,Ishikawa
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- Heteroaryl cinnamic acids as inhibitors of leukotriene biosynthesis
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Compounds having the formula I: STR1 are inhibitors of leukotriene biosynthesis. These compounds are useful as anti-asthmatic, anti-allergic, anti-inflammatory, and cytoprotective agents. They are also useful in treating angina, cerebral spasm, glomerular nephritis, hepatitis, endotoxemia, uveitis, and allograft rejection and in preventing the formation of atherosclerotic plaques.
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- Heteroarylnaphthalenes as inhibitors of leukotriene biosynthesis
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Compounds having the formula I: STR1 are inhibitors of leukotriene biosynthesis. These compounds are useful as anti-asthmatic, anti-allergic, anti-inflammatory, and cytoprotective agents. They are also useful in treating angina, cerebral spasm, glomerular nephritis, hepatitis, endotoxemia, uveitis and allograft rejection and in preventing the formation of atherosclerotic plaques.
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