- A novel method to convert ketones and aldehydes to the corresponding alcohols
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A novel method of converting aldehydes and ketones to the corresponding alcohols based on selective indirective electroreduction was found, in which EtOH was used as a support electrolyte and Al(OC2H5)3 as intermedia that was produced on spot reduction by electrolysis. The reaction took place in a cell with two Al electrodes.
- Wei-Dong, Yang,Chi, Yang,An-Xing, Wu
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Read Online
- Degradation of the neolignan, burchellin in the hemolymph of the bloodsucking insect Rhodnius prolixus
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The neolignan, burchellin, a natural compound that reduces urine excretion in larvae of the bloodsucking bug, Rhodnius prolixus, a vector of Chagas' disease, is rapidly degraded in the hemolymph of the insect. The main product that accumulates in this tissue has been shown to be piperonyl alcohol. Other catabolites have been identified by GC-MS analysis.
- Cabral, Marise M.O.,Garcia, Eloi S.,Gottlieb, Otto R.,Kelecom, Alphonse
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Read Online
- C(sp3)-H Monoarylation of Methanol Enabled by a Bidentate Auxiliary
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With the assistance of a practical directing group (COAQ), the first catalytic protocol for the palladium-catalyzed C(sp3)-H monoarylation of methanol has been developed, offering an invaluable synthesis means to establish extensive derivatives of crucial arylmethanol functional fragments. Furthermore, the gram-scale reaction, broad substrate scope, excellent functional group compatibility, and even the practical synthesis of medicines further demonstrate the usefulness of this strategy.
- Gou, Quan,Ran, Man,Ren, Jian,Tan, Xiaoping,Yuan, Binfang,Yuan, Tengrui,Zhang, Ming-Zhong,Zhang, Xing
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supporting information
p. 118 - 123
(2021/01/13)
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- Oxidation of Primary Alcohols and Aldehydes to Carboxylic Acids via Hydrogen Atom Transfer
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The oxidation of primary alcohols and aldehydes to the corresponding carboxylic acids is a fundamental reaction in organic synthesis. In this paper, we report a new chemoselective process for the oxidation of primary alcohols and aldehydes. This metal-free reaction features a new oxidant, an easy to handle procedure, high isolated yields, and good to excellent functional group tolerance even in the presence of vulnerable secondary alcohols and tert-butanesulfinamides.
- Tan, Wen-Yun,Lu, Yi,Zhao, Jing-Feng,Chen, Wen,Zhang, Hongbin
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supporting information
p. 6648 - 6653
(2021/09/08)
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- Iron-catalyzed chemoselective hydride transfer reactions
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A Diaminocyclopentadienone iron tricarbonyl complex has been applied in chemoselective hydrogen transfer reductions. This bifunctional iron complex demonstrated a broad applicability in mild conditions in various reactions, such as reduction of aldehydes over ketones, reductive alkylation of various functionalized amines with functionalized aldehydes and reduction of α,β-unsaturated ketones into the corresponding saturated ketones. A broad range of functionalized substrates has been isolated in excellent yields with this practical procedure.
- Coufourier, Sébastien,Ndiaye, Daouda,Gaillard, Quentin Gaignard,Bettoni, Léo,Joly, Nicolas,Mbaye, Mbaye Diagne,Poater, Albert,Gaillard, Sylvain,Renaud, Jean-Luc
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supporting information
(2021/06/07)
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- Efficient and chemoselective hydrogenation of aldehydes catalyzed by well-defined PN3-pincer manganese(ii) catalyst precursors: An application in furfural conversion
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Well-defined and air-stable PN3-pincer manganese(ii) complexes were synthesized and used for the hydrogenation of aldehydes into alcohols under mild conditions using MeOH as a solvent. This protocol is applicable for a wide range of aldehydes containing various functional groups. Importantly, α,β-unsaturated aldehydes, including ynals, are hydrogenated with the CC double bond/CC triple bond intact. Our methodology was demonstrated for the conversion of biomass derived feedstocks such as furfural and 5-formylfurfural to furfuryl alcohol and 5-(hydroxymethyl)furfuryl alcohol respectively.
- Gholap, Sandeep Suryabhan,Dakhil, Abdullah Al,Chakraborty, Priyanka,Li, Huaifeng,Dutta, Indranil,Das, Pradip K.,Huang, Kuo-Wei
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supporting information
p. 11815 - 11818
(2021/11/30)
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- Light-driven MPV-type reduction of aryl ketones/aldehydes to alcohols with isopropanol under mild conditions
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Alcohols are versatile structural motifs of pharmaceuticals, agrochemicals and fine chemicals. With respect to green chemistry, the development of more sustainable and cost-efficient processes for converting ketones/aldehydes to alcohols is highly desired. Herein, a direct light-driven strategy for reducing ketones/aldehydes to alcohols using isopropanol as the reducing agent and solvent, in the presence of t-BuOLi, under an air atmosphere at room temperature is developed. This operationally simple light-promoted Meerwein-Ponndorf-Verley (MPV) type reduction can be used to produce various benzylic alcohol derivatives as well as applied to bioactive molecules and PEEK model compounds, demonstrating its application potential.
- Cao, Dawei,Xia, Shumei,Pan, Pan,Zeng, Huiying,Li, Chao-Jun,Peng, Yong
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supporting information
p. 7539 - 7543
(2021/10/12)
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- Method for synthesizing piperonyl alcohol through catalytic hydrogenation
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The invention relates to the technical field of organic chemical synthesis, in particular to a method for synthesizing piperonyl alcohol through catalytic hydrogenation, which comprises the followingsteps of: firstly, adding piperonal solution and Raney nickel into a hydrogenation reaction kettle according to the mass ratio of 1: (0.01-1), and introducing inert gas to replace air in the hydrogenation reaction kettle; and secondly, introducing hydrogen, heating to 30-150 DEG C, carrying out a catalytic hydrogenation reaction under the hydrogen pressure of 0.5-5 MPa, filtering to recover Raneynickel after the reaction is finished, and carrying out reduced pressure distillation on the filtrate to obtain a recovered solvent and a crude piperonyl alcohol product. According to the method, theproblems of expensive catalyst, low production efficiency and high production cost in the synthesis process of the piperonyl alcohol in the prior art are solved, the piperonal and the solvent are mixed and subjected to hydrogenation reduction to form the piperonyl alcohol at a certain pressure and temperature under the catalytic action of Raney nickel, the process yield is high, no three wastes are generated, and the method conforms to the green development trend.
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Paragraph 0024-0035
(2021/02/10)
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- Oxoammonium-Mediated Allylsilane–Ether Coupling Reaction
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A new C(sp3)?H functionalization reaction consisting of the oxidative α-allylation of allyl- and benzyl- methyl ethers has been developed. The C?C coupling could be carried out under mild conditions thanks to the use of cheap and green oxoammonium salts. The scope of the reaction was studied over 27 examples, considering the nature of the substituents on the two coupling partners.
- Carlet, Federica,Bertarini, Greta,Broggini, Gianluigi,Pradal, Alexandre,Poli, Giovanni
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supporting information
p. 2162 - 2168
(2021/04/02)
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- KMnO4-catalyzed chemoselective deprotection of acetate and controllable deacetylation-oxidation in one pot
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A novel and efficient protocol for chemoselective deacetylation under ambient conditions was developed using catalytic KMnO4. The stoichiometric use of KMnO4 highlighted the dual role of a heterogeneous oxidant enabling direct access to aromatic aldehydes in one-pot sequential deacetylation-oxidation. The reaction employed an alternative solvent system and allowed the clean transformation of benzyl acetate to sensitive aldehyde in a single step while preventing over-oxidation to acids. Use of inexpensive and readily accessible KMnO4 as an environmentally benign reagent and the ease of the reaction operation were particularly attractive, and enabled the controlled oxidation and facile cleavage of acetate in a preceding step. This journal is
- Gurawa, Aakanksha,Kumar, Manoj,Rao, Dodla S.,Kashyap, Sudhir
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supporting information
p. 16702 - 16707
(2020/10/27)
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- Amino Benzamidoxime (ABAO)-Based Assay to Identify Efficient Aldehyde-Producing Pichia pastoris Clones
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The chemoselective synthesis of aldehydes is a challenging task. Nature provides carboxylic acid reductases (CARs) as elegant tools for the direct reduction of carboxylic acids to their respective aldehydes. The discovery of new CARs and strains that efficiently produce these enzymes necessitates a robust high-throughput assay with selectivity for aldehydes. We recently reported a simple assay that allows the substrate independent and chemoselective quantification of aldehydes (irrespective of their chemical structure). The assay utilized amino benzamidoxime (ABAO), which forms UV-active and fluorescent dihydroquinazolines. In this study, we adapted the ABAO-assay for the identification and comparison of Pichia pastoris clones with the ability to produce aldehydes from carboxylic acids. Specifically, CAR and PPTase from Mycobacterium marinum (MmCAR and MmPPTase) were co-expressed using different bidirectional promoters (BDPs). A library of 598 clones was screened for piperonal production with the ABAO assay and the results were validated by HPLC quantification. 1 OD unit of the best Pichia pastoris clone 2.A7, regulating MmCAR and MmPPTase expression by two strong constitutive promoters, fully converted 5 mM of piperonylic acid within 2 h. (Figure presented.).
- Horvat, Melissa,Larch, Tanja-Saskia,Rudroff, Florian,Winkler, Margit
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supporting information
p. 4673 - 4679
(2020/10/02)
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- Erratum: Redox-Noninnocent Ligand-Supported Vanadium Catalysts for the Chemoselective Reduction of C=X (X = O, N) Functionalities (Journal of the American Chemical Society (2019) 141:38 (15230-15239) DOI: 10.1021/jacs.9b07062)
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Pages 15232, 15233, and 15236. In the original paper, the doublet wave functions for 21 and 21a/21b were incorrectly (Figure Presented). reported as spin-contaminated in sections 2.3 and 2.8 (Figure 3 and Scheme 9, respectively.) This comes from the incorrectly reported expected eigenvalue of 0.75 for the spin-squared operator ??2? for the antiferromagnetically coupled doublet |↓?L|↑↑?V state (originally given in the Supporting Information). The correct expected eigenvalue for the |↓?L|↑↑?V state should be 1.75. The wave functions for 21 and 21a/21b (eigenvalues 1.79 and 1.77/1.66, respectively) are therefore not spincontaminated. The corrected Figure 3 and Scheme 9 are presented below. A corrected Supporting Information file is also provided. The corrections do not affect any of the conclusions of the Article, but slightly decrease the gap between the quartet and doublet spin surfaces. Scheme 3 has been also corrected to reflect the fact that (CH3)3SiCH2 ? radicals can only react based on spin conservation.
- Zhang, Guoqi,Wu, Jing,Zheng, Shengping,Neary, Michelle C.,Mao, Jincheng,Flores, Marco,Trovitch, Ryan J.,Dub, Pavel A.
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supporting information
p. 16507 - 16509
(2020/10/14)
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- Cyclopentadienone iron tricarbonyl complexes-catalyzed hydrogen transfer in water
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The development of efficient and low-cost catalytic systems is important for the replacement of robust noble metal complexes. The synthesis and application of a stable, phosphine-free, water-soluble cyclopentadienone iron tricarbonyl complex in the reduction of polarized double bonds in pure water is reported. In the presence of cationic bifunctional iron complexes, a variety of alcohols and amines were prepared in good yields under mild reaction conditions.
- Coufourier, Sébastien,Gaillard, Sylvain,Mbaye, Mbaye Diagne,Ndiaye, Daouda,Renaud, Jean-Luc
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supporting information
(2020/01/28)
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- Reduction over Condensation of Carbonyl Compounds through a Transient Hemiaminal Intermediate Using Hydrazine
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Reduction of carbonyl moieties to the corresponding alcohol using simply hydrazine hydrate has been considerably unfeasible until now due to the well-known condensation reaction. However, herein, we report that using an excess of 20-fold equivalents, the reduction proceeds in excellent yields. 1H NMR study of the reaction and density functional theory (DFT) calculations indicate that the final fate of the hemiaminal intermediate is crucial to obtain the alcohol or the hydrazone.
- Vilches-Herrera, Marcelo,Gallardo-Fuentes, Sebastián,Aravena-Opitz, Mauricio,Yá?ez-Sánchez, Mauricio,Jiao, Haijun,Holz, Jens,B?rner, Armin,Lühr, Susan
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p. 9213 - 9218
(2020/08/14)
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- One-pot chemoenzymatic reactions in water enabled by micellar encapsulation
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The use of micellar conditions to enable one-pot reactions involving both transition metal and enzymatic catalysts is reported. Representative enzymatic transformations under micellar conditions are unaffected by the presence of non-ionic surfactants, including designer surfactants such as TPGS-750-M. Furthermore, the presence of enzymes has a negligible effect on transition metal catalysis under micellar conditions in water. Finally, three one-pot chemoenzymatic reactions in water are reported in which the micelle-forming surfactant TPGS-750-M is a crucial factor for reaction efficiency.
- Adams, Nicholas P.,Bushi, Jurgen,Hastings, Courtney J.,Kolb, Samuel J.
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supporting information
p. 6187 - 6193
(2020/10/18)
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- Benzopentaoxyheterocycle-benzimidazole salt compounds, and synthesis method and application thereof
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The invention discloses benzopentaoxyheterocycle-benzimidazole salt compounds, and a synthesis method and an application thereof, and belongs to the technical field of medicinal chemistry. The structural formula of the benzopentaoxyheterocycle-benzimidazole salt compounds is shown in the description. In the formula, when X is O and Y is CH2, R and R are H, and R is a 2-naphthoylmethyl group, or R is CH3, R is H, and R is a 2-naphthoylmethyl group, a 4-bromobenzyl, a 2-naphthylmethyl group, a 4-methylbenzyl group or a 2-bromobenzyl group; when X is CH2 and Y is C-O, R and R are H, and R is a 2-naphthoylmethyl group, or R is CH3, R is H, and R is a 2-naphthoylmethyl group, or R is H, R is CH3, and R is a 2-naphthoylmethyl group or a 2-bromobenzylgroup; and when X is CH2 and Y is CH2, R is H, R is CH3, and R is a 2-naphthoylmethyl group or a 2-bromobenzyl group. Medicines prepared from the compounds of the invention and at least one pharmaceutically acceptable excipient, diluent or carrier can be used for tumor cancers.
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Paragraph 0034; 0036-0040; 0049-0054; 0063-0067; 0076-0080
(2019/11/04)
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- Selective Deprotection of the Diphenylmethylsilyl (DPMS) Hydroxyl Protecting Group under Environmentally Responsible, Aqueous Conditions
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Two new methods for selective deprotection of diphenylmethylsilyl (DPMS) ethers are described. Unmasking can be achieved with either catalytic amounts of perfluoro-1-butanesulfonyl fluoride (a SuFEx reagent) under mild, aqueous micellar conditions, or using stoichiometric amounts of 18-crown-6 ether in aqueous ethanol.
- Akporji, Nnamdi,Lieberman, Josh,Maser, Michael,Yoshimura, Masahiko,Boskovic, Zarko,Lipshutz, Bruce H.
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p. 5743 - 5747
(2019/11/11)
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- Controlled Reduction of Carboxamides to Alcohols or Amines by Zinc Hydrides
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New protocols for controlled reduction of carboxamides to either alcohols or amines were established using a combination of sodium hydride (NaH) and zinc halides (ZnX2). Use of a different halide on ZnX2 dictates the selectivity, wherein the NaH-ZnI2 system delivers alcohols and NaH-ZnCl2 gives amines. Extensive mechanistic studies by experimental and theoretical approaches imply that polymeric zinc hydride (ZnH2)∞ is responsible for alcohol formation, whereas dimeric zinc chloride hydride (H?Zn?Cl)2 is the key species for the production of amines.
- Ong, Derek Yiren,Yen, Zhihao,Yoshii, Asami,Revillo Imbernon, Julia,Takita, Ryo,Chiba, Shunsuke
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supporting information
p. 4992 - 4997
(2019/03/13)
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- Ir(bis-NHC)-Catalyzed Direct Conversion of Amines to Alcohols in Aqueous Glycerol
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Sustainable catalytic conversion of amines to alcohols was realized in the presence of iridium catalysts and aqueous glycerol. Iridium catalysts involving bis-N-heterocyclic carbene (bis-NHC) show good reactivity and stability in the conversion of amines into alcohols in aqueous glycerol. The reaction was initiated with the dehydrogenation of amines and followed by hydrolysis and reduction. Iridium catalysts play dual roles in both the dehydrogenation and reduction steps. By employing glycerol as a solvent and hydrogen source, the final reduction was facilitated. The synthesis and characterization of various Ir(bis-NHC) complexes are described along with the catalytic reaction results of the amine into alcohol conversion.
- Cheong, Yeon-Joo,Lee, Seunghyeon,Hwang, Sang Joon,Yoon, Woojin,Yun, Hoseop,Jang, Hye-Young
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supporting information
p. 1940 - 1943
(2019/02/25)
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- Enzymatic One-Step Reduction of Carboxylates to Aldehydes with Cell-Free Regeneration of ATP and NADPH
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The direct generation of aldehydes from carboxylic acids is often a challenging synthetic task but undoubtedly attractive in view of abundant supply of such feedstocks from nature. Though long known, biocatalytic carboxylate reductions are at an early stage of development, presumably because of their co-factor requirement. To establish an alternative to whole-cell-based carboxylate reductions which are limited by side reactions, we developed an in vitro multi-enzyme system that allows for quantitative reductions of various carboxylic acids with full recycling of all cofactors and prevention of undesired over-reductions. Regeneration of adenosine 5′-triphosphate is achieved through the simultaneous action of polyphosphate kinases from Meiothermus ruber and Sinorhizobium meliloti and β-nicotinamide adenine dinucleotide 2′-phosphate is reduced by a glucose dehydrogenase. Under these conditions and in the presence of the carboxylate reductases from Neurospora crassa or Nocardia iowensis, various aromatic, heterocyclic and aliphatic carboxylic acids were quantitatively reduced to the respective aldehydes.
- Strohmeier, Gernot A.,Eitelj?rg, Inge C.,Schwarz, Anna,Winkler, Margit
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p. 6119 - 6123
(2019/04/13)
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- Practical and selective hydroboration of aldehydes and ketones in air catalysed by an iron(ii) coordination polymer
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The in air catalytic hydroboration of ketones and aldehydes with pinacolborane by an iron(ii) coordination polymer (CP) is carried out under mild and solvent-free conditions. The precatalyst is highly active towards a wide range of substrates including functionalized ketones and aldehydes in the presence of KOtBu as an activator, achieving a high turnover number (TON) of up to 9500. Excellent chemoselectivity to aldehydes over ketones was also revealed, which is in sharp contrast with the results obtained under inert atmosphere using the same catalyst system. This catalyst observed here is not only highly efficient but also recyclable for reuse for at least 5 times without losing its effectiveness.
- Zhang, Guoqi,Cheng, Jessica,Davis, Kezia,Bonifacio, Mary Grace,Zajaczkowski, Cynthia
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p. 1114 - 1121
(2019/03/12)
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- Borinic Acid Mediated Hydrosilylations: Reductions of Carbonyl Derivatives
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4-Fluoro-2-chlorophenylborinic acid acts as a precatalyst in the presence of phenylsilane for the facile reduction of ketones, aldehydes and imines. Notably, synergistic mediation of a tertiary amine was found essential to trigger silicon to boron hydride transfer to generate a key amine–diarylhydroborane Lewis complex.
- Chardon, Aurélien,Rouden, Jacques,Blanchet, Jér?me
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supporting information
p. 995 - 998
(2018/12/13)
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- Cobalt(II) Coordination Polymer as a Precatalyst for Selective Hydroboration of Aldehydes, Ketones, and Imines
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Highly effective hydroboration precatalyst is developed based on a cobalt(II)-terpyridine coordination polymer (CP). The hydroboration of ketones, aldehydes, and imines with pinacolborane (HBpin) has been achieved using the recyclable CP catalyst in the presence of an air-stable activator. A wide range of substrates containing polar C=O or C=N bonds have been hydroborated selectively in excellent yields under ambient conditions.
- Wu, Jing,Zeng, Haisu,Cheng, Jessica,Zheng, Shengping,Golen, James A.,Manke, David R.,Zhang, Guoqi
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p. 9442 - 9448
(2018/07/05)
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- Synthetic method for dihydrostilbenes and anti-inflammatory compounds containing thereof
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The present invention aims to provide an effective anti-inflammatory agent without side effects. The present inventors have invented a method for efficiently synthesizing dihydrostilbene and derivatives (compounds 1 to 5) from starting materials at a high yield. In addition, the anti-inflammatory effects were evaluated in LPS-induced RAW-264.7 macrophages. The compounds of dihydrostilbene do not exhibit cytotoxicity and are shown to weakly or well inhibit nitric oxide production induced by LPS at the concentration of 10 andmu;M.COPYRIGHT KIPO 2018
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Paragraph 0104; 0137; 0138; 0141; 0146; 0147
(2018/05/03)
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- A heterocyclic compound and use thereof
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The invention discloses a compound of a general formula I and application of the compound serving as a plant disease-resistance activator. In the formula, a substituent group R1 and 0-3 substituent groups R2 exist on the 4th, 5th, 6th and 7th sites; R1 is independently selected from -R3OOH, -R4OOR5, -R6OH and -R7-O-R8; R2 is independently selected from C1-C6 alkyl, C1-6 halogenated alkyl, C1-C6 alkoxy, C1-C6 halogenated alkoxy, hydroxyl, halogen, nitro, amino and C1-C6 alkylamino; R3, R4, R5, R6, R7 and R8 are independently selected from C1-C6 alkyl and C1-6 halogenated alkyl. The compound induces plants to generate disease resistance so as to inhibit pathogens instead of directly killing or inhibiting the pathogens. The compound has the advantages of systematicness, durability, broad spectrum, high safety and the like, so the amount of highly toxic pesticides can be reduced, and the compound is environmentally friendly and has huge industrialized and commercial prospects and market values.
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Paragraph 0103-0105; 0107; 0117-0119
(2018/05/24)
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- Syntheses of hydrido selenophenolato iron(II) complexes and their catalytic application in hydrosilylation of aldehydes and ketones
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Three novel selenophenolato hydrido iron(II) complexes [cis-(H)(SeAr)Fe(PMe3)4] (4–6) (Ar=C6H5 (4), p-MeOC6H4 (5) and o-MeC6H4 (6)) were prepared through the reaction of Fe(PMe3)4 with selenophenols ArSeH (1–3) via Se–H activation. The iron hydrido complexes 4, 5 and 6 could catalyze the hydrosilylation of aldehydes and ketones. Among them complex 5 is the best catalyst for this process. Furthermore, α,β-unsaturated alcohols could be obtained from the selective reduction reactions of the corresponding α,β-unsaturated carbonyls catalyzed by hydrido iron(II) complex 5. This catalytic system has good tolerance for some common groups but it is easy to reduce the nitro group to an amino group. The experiments indicate that the chemoselectivity for this catalytic system is –CHO>–NO2>–C([dbnd]O)CH3. The crystal structure of 6 was determined by X-ray diffraction.
- Wang, Yangyang,Ren, Shishuai,Zhang, Wenbo,Xue, Benjing,Qi, Xinghao,Sun, Hongjian,Li, Xiaoyan,Fuhr, Olaf,Fenske, Dieter
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- Porous burnt zirconium phosphate catalyst and its application in the hydrogenation in Piperonal (by machine translation)
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The invention discloses a porous pyrophosphoric acid zirconium catalyst and its application in the hydrogenation in Piperonal, belongs to the technical field of solid acid catalysis. The catalyst prepared by the method of simple synthesis steps, to the use of the raw material is cheap, the obtained catalyst itself carrying a large number of acid sites and alkaline site, can be high-efficient catalytic reduction Piperonal was the carbon. After the reaction catalyst is easy to separate, can be recycled many times, and meets the green and the demand for sustainable development. (by machine translation)
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Paragraph 0030-0033; 0034-0037; 0038-0041; 0042-0049
(2018/08/03)
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- Density functional theory calculations, vibration spectral analysis and molecular docking of the antimicrobial agent 6-(1,3-benzodioxol-5-ylmethyl)-5-ethyl-2-{[2-(morpholin-4-yl)ethyl] sulfanyl}pyrimidin-4(3H)-one
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Vibrational spectral analysis and quantum chemical computations based on density functional theory have been performed on the antimicrobial agent 6-(1,3-benzodioxol-5-ylmethyl)-5-ethyl-2-{[2-(morpholin-4-yl)ethyl]sulfanyl}pyrimidin-4-(3H)-one. The equilibrium structural geometry, various bonding features and harmonic vibrational wavenumbers of the title compound have been investigated using DFT-B3LYP function at 6-311++G(d,p) basis set. The detailed interpretations of the vibrational spectra have been carried out with the aid of VEDA 4 program. The various intramolecular interactions of the title compound have been exposed by natural bond orbital analysis. The FT-IR and FT-Raman spectra of the title molecule have been recorded and analyzed. Blue-shifting of the C-H wavenumber along with a decrease in the C-H bond length attribute for the formation of the C-H...O hydrogen bonding provide an evidence for a charge transfer interaction. Also, the distribution of natural atomic charges reflects the presence of intramolecular hydrogen bonding. The analysis of the electron density of HOMO and LUMO gives an idea of the delocalization and the low value of energy gap indicates electron transfer within the molecule. Moreover, molecular docking studies revealed the possible binding of the title molecule to different antimicrobial target proteins.
- Almutairi, Maha S.,Soumya,Al-Wabli, Reem I.,Hubert Joe,Attia, Mohamed I.
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p. 653 - 666
(2020/03/30)
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- Preparation and reactions of certain racemic and optically active cyanohydrins derived from 2-chlorobenzaldehyde, 4-fluorobenzaldehyde, benzo[d][1,3]-dioxole-5-carbaldehyde and 2,3-dihydrobenzo[b][1,4]dioxine-6-carbaldehyde. Antimicrobial and in vitro antitumor evaluation of the products
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THE CHEMOENZYMATIC reaction of selected aldehydes, namely 2-chlorobenzaldehyde (1a), 4-fluorobenzaldehyde (1b), benzo[d][1,3]dioxole-5-carbaldehyde (1c) and/or 2,3-dihydrobenzo [b] [1,4] dioxine-6-carbaldehyde (1d) with hydrogen cyanide in presence of (R)-oxynitrilase (R)-Pa HNL [EC 4.1.2.10] from almonds, as a chiral catalyst, gave the optically active cyanohydrin enantiomers ( R)-2a-c, respectively. Acetone cyanohydrin (3), was also used, as a transcyanating agent, to give the same products. The racemic cyanohydrins (R,S)-2a-d have been synthesized, as well, by treating compounds 1a-d with aqueous potassium cyanide solution in presence of a saturated solution of sodium metabisulphite (Na2S2O5). The optical purity of cyanohydrins (R)-2a-c was determined through their derivatization with (S)-naproxen chloride (S)-5 to the respective diastereomers (R,2S)-6a-c which were obtained in diastereomeric excess (de) values up to 93 % (1H NMR). Heating compounds (R)-2a,b and / or their racemic analogues (R,S)-2a-c with concentrated hydrochloric acid gave the respective α-hydroxycarboxylic acids 7a-c. Moreover, reduction of cyanohydrins (R,S)-2b,c under different conditions resulted in a hydrodecyanation giving the respective primary alcohols 8a,b. Structures and configurations of the new compounds were confirmed with compatible elementary microanalyses and spectroscopic (IR, 1H NMR, 13C NMR, MS and single crystal X-ray crystallography) measurements. The antimicrobial activity of derivatives 6a-d against four bacterial species (Bacillus subtilis, Staphylococcus aureus, Escherichia coli and Pseudomonas aeruginosa) and two fungi (Aspergillus flavus and Candida albicans) were undertaken. Moreover, compounds (R,2S)-6b, (R,2S)(S,2S)-6b and (R,2S)-6c were screened for their in virto antitumor activity against three human solid cancer cell lines (HCT 116, HepG2 and MCF-7). In general, the tested compounds were found inactive or showed weak activities in comparison with the standard drugs.
- Yosef, Hisham Abdallah A.,Elmasry,Ibrahim, Nabila M.,Ismael, Eman H. I.,Mahran
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p. 301 - 328
(2017/06/08)
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- Aryloxyphenoxies propionate compound and its preparation method and application
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The invention discloses a piperonyl-containing aryloxyphenoxies propionate compound, which has the following structure: the formula is shown in the specification. The specific preparation method includes steps of taking catechol as raw material, and compounding heliotropin through two-step reaction; performing reduction reaction with NaBH4 to prepare 3, 4- methylenedioxy phemethylol; reacting 2-(4-aryloxyphenoxies) propionyl chloride with prepare 3, 4- methylenedioxy phemethylol to prepare two piperonyl-containing aryloxyphenoxies propionate compounds. The compound has good weeding activity; especially, the weeding activity of monocotyledon weed is better than that of dicotyledonous weed; the preparation method is simple to operate, and the yield is high.
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- Aryloxy-phenoxy propionate compounds and preparation method and application thereof
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The invention discloses aryloxy-phenoxy propionate compounds containing piperonyl. The compounds have a following structure. The preparation method specifically includes following preparation steps: using catechol as a raw material; synthesizing heliotropin through two-step reaction; enabling heliotropin to be in reductive reaction with NaBH4 to prepare 3, 4-methylene dioxybenzyl alcohol; enabling 2-(4-aromatic oxygen phenyl) propionyl chloride to react with 3, 4-methylene dioxybenzyl alcohol to prepare two aryloxy-phenoxy propionate compounds containing piperonyl. The compounds have higher weeding activity, especially for monocotyledon weed than dicotyledon weed. The preparation method is simple to operate and high in yield.
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- A heliotropin synthetic method
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The invention relates to the technical field of the medical intermediate fine chemical industry and in particular relates to a synthetic method of piperonal. The synthetic method comprises the following steps: 1 uniformly mixing benzodioxole, formaldehyde with concentration of 40% and a primary catalyst dodecyl trimethyl ammonium bromide with a solvent, then adding hydrochloric acid with concentration of 35-37% and standing for layering after reaction, thus obtaining a piperonyl chloride solution, wherein the solvent is trichloromethane, tetrachloromethane or methylbenzene; 2 preparing a sodium bicarbonate or sodium carbonate water solution with concentration less than or equal to that of a saturated solution, adding the sodium bicarbonate or sodium carbonate water solution to the piperonyl chloride solution and reacting to obtain a piperonyl alcohol solution; 3 introducing air into the piperonyl alcohol solution to oxidize the piperonyl alcohol solution to generate a piperonal solution by using both ferric nitrate and 4-hydroxy-2,2,4,4-methylpiperidine nitroxyl free radical as final catalysts. The synthetic method provided by the invention has the advantages of accessible raw materials, mild reaction conditions, stable and high yield, few byproducts and low cost.
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- Prospective Evaluation of Free Energy Calculations for the Prioritization of Cathepsin L Inhibitors
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Improving the binding affinity of a chemical series by systematically probing one of its exit vectors is a medicinal chemistry activity that can benefit from molecular modeling input. Herein, we compare the effectiveness of four approaches in prioritizing building blocks with better potency: selection by a medicinal chemist, manual modeling, docking followed by manual filtering, and free energy calculations (FEP). Our study focused on identifying novel substituents for the apolar S2 pocket of cathepsin L and was conducted entirely in a prospective manner with synthesis and activity determination of 36 novel compounds. We found that FEP selected compounds with improved affinity for 8 out of 10 picks compared to 1 out of 10 for the other approaches. From this result and other additional analyses, we conclude that FEP can be a useful approach to guide this type of medicinal chemistry optimization once it has been validated for the system under consideration.
- Kuhn, Bernd,Tichy, Michal,Wang, Lingle,Robinson, Shaughnessy,Martin, Rainer E.,Kuglstatter, Andreas,Benz, J?rg,Giroud, Maude,Schirmeister, Tanja,Abel, Robert,Diederich, Fran?ois,Hert, Jér?me
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p. 2485 - 2497
(2017/04/03)
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- Accessing N-Acyl Azoles via Oxoammonium Salt-Mediated Oxidative Amidation
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An operationally simple, robust, metal-free approach to the synthesis of N-acyl azoles from both alcohols and aldehydes is described. Oxidative amidation is facilitated by a commercially available organic oxidant (4-acetamido-2,2,6,6-tetramethylpiperidine-1-oxoammonium tetrafluoroborate) and proceeds under very mild conditions for an array of structurally diverse substrates. Tandem reactions of these activated amides, such as transamidation and esterification, enable further elaboration. Also, the spent oxidant can be recovered and used to regenerate the oxoammonium salt.
- Ovian, John M.,Kelly, Christopher B.,Pistritto, Vincent A.,Leadbeater, Nicholas E.
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supporting information
p. 1286 - 1289
(2017/03/22)
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- Harnessing the Reactivity of Iridium Hydrides by Air: Iridium-Catalyzed Oxidation of Aldehydes to Acids in Water
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An iridium-catalyzed oxidation of aldehydes to acids was realized by using air as the oxidant and water as the solvent in the presence of base. Interestingly, the same type of catalysts were also used for the reduction of aldehydes under acidic conditions. A common iridium hydride intermediate is proposed for both redox reactions. The oxidation has a number of advantages such as high yields, great functionality tolerance, and easy purification without chromatography.
- Yang, Zhanhui,Luo, Renshi,Zhu, Zhongpeng,Yang, Xuerong,Tang, Weiping
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supporting information
p. 4095 - 4098
(2017/11/21)
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- Chemoselective continuous-flow hydrogenation of aldehydes catalyzed by platinum nanoparticles dispersed in an amphiphilic resin
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A chemoselective continuous-flow hydrogenation of aldehydes catalyzed by a dispersion of platinum nanoparticles in an amphiphilic polymer (ARP-Pt) has been developed. Aromatic and aliphatic aldehydes bearing various reducible functional groups, such as keto, ester, or amide groups, readily underwent flow hydrogenation in aqueous solutions within 22 s in a continuous-flow system containing ARP-Pt to give the corresponding primary benzylic or aliphatic alcohols in ≤99% yield with excellent chemoselectivity. Moreover, the long-term continuous-flow hydrogenation of benzaldehyde for 8 days was realized, and the total turnover number of the catalyst reached 997. The flow hydrogenation system provides an efficient and practical method for the chemoselective hydrogenation of aldehydes bearing reducible functional groups.
- Osako, Takao,Torii, Kaoru,Hirata, Shuichi,Uozumi, Yasuhiro
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p. 7371 - 7377
(2017/11/09)
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- Selective Enzymatic Transformation to Aldehydes in vivo by Fungal Carboxylate Reductase from Neurospora crassa
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The enzymatic reduction of carboxylic acids is in its infancy with only a handful of biocatalysts available to this end. We have increased the spectrum of carboxylate-reducing enzymes (CARs) with the sequence of a fungal CAR from Neurospora crassa OR74A (NcCAR). NcCAR was efficiently expressed in E. coli using an autoinduction protocol at low temperature. It was purified and characterized in vitro, revealing a broad substrate acceptance, a pH optimum at pH 5.5–6.0, a Tmof 45 °C and inhibition by the co-product pyrophosphate which can be alleviated by the addition of pyrophosphatase. The synthetic utility of NcCAR was demonstrated in a whole-cell biotransformation using the Escherichia coli K-12 MG1655 RARE strain in order to suppress overreduction to undesired alcohol. The fragrance compound piperonal was prepared from piperonylic acid (30 mM) on gram scale in 92 % isolated yield in >98% purity. This corresponds to a productivity of 1.5 g/L/h. (Figure presented.).
- Schwendenwein, Daniel,Fiume, Giuseppe,Weber, Hansj?rg,Rudroff, Florian,Winkler, Margit
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supporting information
p. 3414 - 3421
(2016/11/13)
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- Highly Selective Hydroboration of Alkenes, Ketones and Aldehydes Catalyzed by a Well-Defined Manganese Complex
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Well-defined manganese complexes based on inexpensive, readily available ligands, 2,2′:6′,2′′-terpyridine and its derivatives have been prepared and employed for the selective hydroboration of alkenes, ketones and aldehydes. Highly Markovnikov regioselective hydroboration of styrenes as well as excellent chemoselective hydroboration of ketones over alkenes were achieved, for the first time, by an earth-abundant manganese catalyst.
- Zhang, Guoqi,Zeng, Haisu,Wu, Jing,Yin, Zhiwei,Zheng, Shengping,Fettinger, James C.
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supporting information
p. 14369 - 14372
(2016/11/11)
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- Dihydrostilbenes and diarylpropanes: Synthesis and in vitro pharmacological evaluation as potent nitric oxide production inhibition agents
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An efficient synthesis of dihydrostilbenes (1–5) and diarylpropanes (6–10) is achieved from the commercially available starting materials and Wittig-Horner reaction, Claisen–Schmidt condensation and hydrogenation as key steps. Later, their nitric oxide (NO) production inhibition effects were evaluated in lipopolysaccharide (LPS)-induced RAW-264.7 macrophages as an indicator of anti-inflammatory activity. All the tested compounds significantly decreased NO production in a concentration-dependent manner except compounds 2, 6 and 8 and did not show notable cytotoxicity except compound 1. Two compounds i.e., compound 9 (hindsiipropane B) (100%; IC50?=?1.84?μM) possessed the most potent NO inhibitory activity which was even stronger than the positive control, L-NMMA (90.1%; IC50?=?2.73?μM) followed by compound 4 (75.5%; IC50?=?2.98?μM) at 10?μM concentration and this finding was also further correlated by suppressed expression of LPS stimulated inducible NO synthase. Our study revealed that compound 9, a 1,3-diarylpropane scaffold with 3″,4″-dimethoxyphenyl and 3′,4′-dihydroxy-2′-methoxyphenyl motifs could be considered as potential compound or lead compound for further development of NO production-targeted anti-inflammatory agents.
- Jang, Ha Young,Park, Hyeong Jin,Damodar, Kongara,Kim, Jin-Kyung,Jun, Jong-Gab
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supporting information
p. 5438 - 5443
(2016/11/09)
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- Vanadium-Catalyzed Oxidative Debenzylation of O-Benzyl Ethers at ppm Level
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An advantageous methodology for the oxidative debenzylation of ethers has been developed. Very low amounts of a catalyst system based on vanadyl acetylacetonate and a triazole type pincer ligand allow the selective oxidative cleavage of a number of O-benzyl ethers in the presence of oxygen as the sole oxidant. The methodology tolerates a number of functional groups such as halo-, alkoxy-, or trifluoromethylarenes, alkyne, alkene, ether, and acetal units. Large-scale deprotections can be also carried out by the optimized procedure, which is amenable to enantioenriched reactants as well. (Figure presented.).
- Urgoitia, Garazi,SanMartin, Raul,Herrero, María Teresa,Domínguez, Esther
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p. 3307 - 3312
(2016/10/21)
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- One-pot synthesis of N-substituted β-amino alcohols from aldehydes and isocyanides
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A practical two-stage one-pot synthesis of N-substituted β-amino alcohols using aldehydes and isocyanides as starting materials has been developed. This method features mild reaction conditions, broad scope, and general tolerance of functional groups. Based on a less common central carbon-carbon bond disconnection, this protocol complements traditional approaches that involve amines and various carbon electrophiles (epoxides, α-halo ketones, β-halohydrins). Medicinally relevant products can be prepared in a concise and efficient way from simple building blocks, as demonstrated in the synthesis of the antiasthma drug salbutamol. Upgrading the synthesis to an enantioselective variant is also feasible.
- Cioc, R?zvan C.,Van Der Niet, Daan J. H.,Janssen, Elwin,Ruijter, Eelco,Orru, Romano V.A.
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supporting information
p. 7808 - 7813
(2015/05/20)
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- Chemoselective deprotection and deprotection with concomitant reduction of 1,3-dioxolanes, acetals and ketals using nickel boride
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An efficient and mild methodology for the reductive deprotection of 1,3-dioxolanes, acetals and ketals to the corresponding aldehydes/ketones and also deprotection with concomitant reduction to the corresponding alcohols has been achieved in quantitative yields using nickel boride generated in situ from nickel chloride and sodium borohydride in methanol. The reactions are chemoselective as halo, alkoxy and methylenedioxy groups are unaffected.
- Khurana, Jitender M.,Dawra, Kiran,Sharma, Purnima
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p. 12048 - 12051
(2015/02/19)
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- Novel 3,4-methylenedioxyde-6-X-benzaldehyde-thiosemicarbazones: Synthesis and antileishmanial effects against Leishmania amazonensis
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A series of eleven 3,4-methylenedioxyde-6-X-benzaldehyde-thiosemicarbazones (16-27) was synthesised as part of a study to search for potential new drugs with a leishmanicidal effect. The thiosemicarbazones, ten of which are new compounds, were prepared in good yields (85-98%) by the reaction of 3,4-methylenedioxyde-6-benzaldehydes (6-X-piperonal), previously synthesised for this work by several methodologies, and thiosemicarbazide in ethanol with a few drops of H2SO4. These compounds were evaluated against Leishmania amazonensis promastigotes, and derivatives where X = I (22) and X = CN (23) moieties showed impressive results, having IC50 = 20.74 μM and 16.40 μM, respectively. The intracellular amastigotes assays showed IC50 = 22.00 μM (22) and 17.00 μM (23), and selectivity index >5.7 and >7.4, respectively, with a lower toxicity compared to pentamidine (positive control, SI = 4.5). The results obtained from the preliminary QSAR study indicated the hydrophobicity (log P) as a fundamental parameter for the 2D-QSAR linear model. A molecular docking study demonstrated that both compounds interact with flavin mononucleotide (FMN), important binding site of NO synthase.
- De Melos, Jorge Luiz R.,Torres-Santos, Eduardo Caio,Fai?es, Viviane Dos S.,De Nigris Del Cistia, Catarina,Sant'Anna, Carlos Maurício R.,Rodrigues-Santos, Cláudio Eduardo,Echevarria, Aurea
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p. 409 - 417
(2015/09/28)
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- Highly chemoselective hydrogenation of active benzaldehydes to benzyl alcohols catalyzed by bimetallic nanoparticles
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By using novel Pd/Ni bimetallic nanoparticles as a catalyst, the active benzaldehydes were hydrogenated to the corresponding benzyl alcohols as unique products in practical quantitative yields. The undesired catalytic hydrogenolysis of the benzyl alcohol was inhibited completely. By using this hydrogenation as a key step, the total synthesis of the natural product gastrodin was achieved with less total steps and a higher total yield.
- Liu, Chulong,Bao, Hailin,Wang, Dingsheng,Wang, Xinyan,Li, Yadong,Hu, Yuefei
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p. 6460 - 6462
(2015/11/16)
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- Organoborane-Catalyzed Hydrogenation of Unactivated Aldehydes with a Hantzsch Ester as a Synthetic NAD(P)H Analogue
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We have developed a method for the hydrogenation of unactivated aldehydes, using a Hantzsch ester as a NAD(P)H analogue in the presence of an electron-deficient triarylborane as a Lewis acid catalyst. Thus, tris[3,5-bis(trifluoromethyl)phenyl]borane efficiently catalyzes the hydrogenation of aliphatic aldehydes with a Hantzsch ester in 1,4-dioxane at 100 °C to give the corresponding aliphatic primary alcohols in up to 97% yield. Aromatic aldehydes also undergo the hydrogenation, even at 25 °C, to furnish the corresponding aromatic primary alcohols in up to 100% yield.
- Hamasaka, Go,Tsuji, Hiroaki,Uozumi, Yasuhiro
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supporting information
p. 2037 - 2041
(2015/09/01)
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- Highly efficient, general hydrogenation of aldehydes catalyzed by PNP iron pincer complexes
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A general protocol for the synthetically and industrially important hydrogenation of aldehydes to alcohols is reported. The reactions are catalyzed by well-defined iron pincer complexes that are capable of hydrogenation of aliphatic and aromatic aldehydes selectively and efficiently under mild conditions, with unprecedented turnover numbers.
- Zell, Thomas,Ben-David, Yehoshoa,Milstein, David
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p. 822 - 826
(2015/02/19)
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- Discovery of phenoxybutanoic acid derivatives as potent endothelin antagonists with antihypertensive activity
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A series of phenoxybutanoic acid derivatives were synthesized and tested for their antagonistic activity on the contraction of the rat thoracic aortic ring induced by endothelin-1. Preliminary screening results showed that 6e and 6g with benzoheterocycles demonstrated significant antagonistic activities when compared to the reference compound BQ123. The results from additional assays for the binding affinity and selectivity for endothelin receptors showed that 6e was a selective ETA antagonist with a nanomolar IC50. Moreover, 6e was effective in relieving hypoxia-induced pulmonary arterial hypertension and right ventricular weight ratio. Therefore, 6e may have potential for further development as a therapeutic agent for the treatment of cardiovascular diseases.
- Cai, Jin,Liu, Ligang,Hong, Kwon Ho,Wang, Peng,Li, Lushen,Cao, Meng,Sun, Chunlong,Wu, Xiaoqing,Zong, Xi,Chen, Junqing,Ji, Min
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p. 657 - 667
(2015/02/19)
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- Synthesis and biological evaluation of nigranoic acid esters as novel human neutrophil elastase inhibitors
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Human neutrophil elastase (HNE) has been implicated as a major contributor in the pathogenesis of diseases, such as lung disorders and other inflammatory diseases. A series of 12 new nigranoic acid esters were regioselectively synthesised in good yields and evaluated for HNE inhibitory activity. Nigranoic acid exhibited significant inhibitory activity against HNE with the IC50 value of 3.77 M, and six esters displayed considerable inhibitory effects on HNE with IC50 values in the range of 2.61-8.95 M. The nigranoic acid esters having phenyls substituted with bromine and trimethoxyls (3h and 3b) showed stronger inhibitory activity on HNE than nigranoic acid.
- Huang, Guoli,Feng, Li,Liu, Bo,He, Yi,Li, Yiming,Chen, Yegao
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p. 1650 - 1656
(2015/03/05)
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- A concise atroposelective formal synthesis of (-)-steganone
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We describe herein the atroposelective formal synthesis of (-)-steganone, a parent member of Steganotaenia araliacea dibenzocyclooctadiene lignan lactones. Our synthesis features an atropodiastereoselective biaryl Suzuki-Miyaura cross-coupling reaction with de up to 99% using as a chiral auxiliary an enantiopure and efficiently converted β-hydroxy sulfoxide derivative. A highly atroposelective formal synthesis of (-)-steganone is described highlighting the use of an enantiopure sulfoxide as a chiral auxiliary in the Suzuki-Miyaura cross-coupling reaction.
- Yalcouye, Boubacar,Choppin, Sabine,Panossian, Armen,Leroux, Frédéric R.,Colobert, Fran?oise
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p. 6285 - 6294
(2015/03/30)
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- Direct trifluoromethylthiolation of alcohols under mild reaction conditions: Conversion of R-OH into R-SCF3
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A direct process for the trifluoromethylthiolation of allylic and benzylic alcohols under mild conditions has been developed. A wide range of free alcohols underwent nucleophilic substitution in the presence of stable CuSCF3 and BF3·Et2O to give the corresponding products in good to excellent yields.
- Nikolaienko, Pavlo,Pluta, Roman,Rueping, Magnus
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supporting information
p. 9867 - 9870
(2014/08/18)
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- METHODS FOR PHOSPHINE OXIDE REDUCTION IN CATALYTIC WITTIG REACTIONS
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A method for increasing the rate of phosphine oxide reduction, preferably during a Wittig reaction comprising use of an acid additive is provided. A room temperature catalytic Wittig reaction (CWR) the rate of reduction of the phosphine oxide is increased due to the addition of the acid additive is described. Furthermore, the extension of the CWR to semi-stabilized and non-stabilized ylides has been accomplished by utilization of a masked base and/or ylide-tuning.
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Page/Page column 54; 55
(2014/09/29)
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- A versatile total synthesis of 8-oxyberberine and oxohomoberberines
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The total syntheses of 8-oxyberberine and oxohomoberberines were accomplished starting from commercially available 5-bromobenzo[d][1,3]dioxole, piperonal and sesamol in high total yield. The key steps involved a modified Pomeranz-Fritsch reaction and the intramolecular Heck cyclization. This approach is short, convenient and suitable for the preparation of homoberberine analogues.
- He, Yun,Zheng, Yang,Hai, Li,Wu, Yong
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p. 1121 - 1127
(2015/01/16)
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