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Pd/NbOPO4 Multifunctional Catalyst for the Direct Production of Liquid Alkanes from Aldol Adducts of Furans
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Xiao‐Hui Liu Prof. Xue‐Qing Gong Prof. Guan‐Zhong Lu Prof. Yan‐Qin Wang 《Angewandte Chemie (International ed. in English)》2014,53(37):9755-9760
Great efforts have been made to convert renewable biomass into transportation fuels. Herein, we report the novel properties of NbOx‐based catalysts in the hydrodeoxygenation of furan‐derived adducts to liquid alkanes. Excellent activity and stability were observed with almost no decrease in octane yield (>90 % throughout) in a 256 h time‐on‐stream test. Experimental and theoretical studies showed that NbOx species play the key role in C? O bond cleavage. As a multifunctional catalyst, Pd/NbOPO4 plays three roles in the conversion of aldol adducts into alkanes: 1) The noble metal (in this case Pd) is the active center for hydrogenation; 2) NbOx species help to cleave the C? O bond, especially of the tetrahydrofuran ring; and 3) a niobium‐based solid acid catalyzes the dehydration, thus enabling the quantitative conversion of furan‐derived adducts into alkanes under mild conditions. 相似文献
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The present article describes the discovery of a new procedure for aldol condensations for the preparation of α,β-unsaturated carbonyl compounds 1 G. Wittig, H. Pommer, and W. Stilz, German Patent 1199252 (April 5, 1963), BASF; Chem. Abstr. 63, P 1739c (1965). . The scope of this process is demonstrated by many examples, including some from the natural products sector; at the same time, however, these examples also mark its limitations. The metalated Schiff's bases may be classified as ambident anions; this also explains acylations on the nitrogen. A comparison of the new directed aldol condensation with the formation of unsaturated carbonyl compounds through olefination via phosphorylids shows that the latter method fails when a ketone is used as the substrate. This is where the described procedure using metalated Schiff's bases proves its value. 相似文献
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Kentaro Okuma Shinobu Maekawa 《Phosphorus, sulfur, and silicon and the related elements》2013,188(5-6):1357-1361
Abstract Reaction of adamantane-2-thione with propiolic acid gave a novel type of cycloadducts, spiro[adamantane-2,2′-(1,3)-oxathiin]6-one, quantitatively. Thiocamphor and thiofenchone also reacted with propiolic acid to give the corresponding adducts stereoselectively. The observation of second-order reaction kinetics and highly stereoselective addition strongly support a cycloaddition mechanism for the thermal addition. The reaction of selenoketones with propiolic acid afforded a similar cylcoadduct. This is the first example of the reaction of monomeric thiones or selones with acetylenic acids. 相似文献
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Udarov B. G. Klyuev A. Yu. Bei M. P. Yuvchenko A. P. Prokopchuk N. R. 《Russian Journal of Applied Chemistry》2002,75(11):1852-1854
Conditions were found for separation of a mixture of terpenoid-maleic adducts and maleic adduct of resin acids in the form of methyl esters by gas-liquid chromatography. 相似文献
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Svein Morgenlie 《Journal of carbohydrate chemistry》2013,32(4):661-671
Abstract Hydroxides of various alkali and alkaline earth metals have been investigated as catalysts in the triose aldol condensation and the aldol condensation between glyceraldehyde and glycolaldehyde. The proportions of diastereomers are very similar in the different product mixtures. Mechanistic models, previously suggested for other aldol condensations, have been considered for the reaction, and the observed diastereoselectivity is in accordance with a pericyclic transition state formed from a cis-enediolate-attack on the aldehyde. 相似文献
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Aldol Condensation of Acetylferrocene under Ultrasound 总被引:2,自引:0,他引:2
ShunJunJI ZhiLiangSHEN ShunYiWANG 《中国化学快报》2003,14(7):663-666
Aldol condensation of acetylferrocene with aromatic aldehydes afforded ferroceny-lenones in 76%-92% yields under ultrasound at room temperature. 相似文献
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The construction of C-C bonds with complete control of the stereochemical course of a reaction is of utmost importance for organic synthesis. The aldol reaction-the simple addition of an enolate donor to a carbonyl acceptor-is one of the most powerful reactions available to the synthetic chemist. In general, control of the relative and absolute configuration of the newly formed stereogenic centers has been achieved through the use of chiral starting materials or chiral auxiliaries. In recent years the search for catalytic methods that efficiently and effectively transfer chirality information has become a major effort in synthetic organic chemistry. Two different approaches have been taken toward the catalytic asymmetric aldol reaction: biocatalysis and catalysis with small molecules. Both approaches have specific advantages and limitations, and as a result are complementary to each other. The important efforts toward both approaches are reviewed in this article. 相似文献
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Louis A. Silks III David B. Kimball Duane Hatch Morgane Ollivault-Shiflett Ryszard Michalczyk Eddie Moody 《合成通讯》2013,43(4):641-653
The chiral oxazolidineselone functionality was found to be an excellent partner in the stereospecific acetate aldol reaction with aldehydes via the titanium enolates. Good stereocontrol was obtained as determined by NMR spectroscopy. The oxazolidineselone also provided a straightforward way to establish the stereopurity of the coupling reaction through 77Se NMR spectroscopy. 相似文献
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Addition of an aldehyde and zinc chloride to a cyclobutanone enolate, prepared by the reaction of an α-chlorocyclobutanone with dimethylcopperlithium, gave an aldol adduct in good yield. 相似文献
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Dr. Karin Weidner Dr. Naoya Kumagai Prof. Dr. Masakatsu Shibasaki 《Angewandte Chemie (International ed. in English)》2014,53(24):6150-6154
The direct catalytic asymmetric aldol reaction offers efficient access to β‐hydroxy carbonyl entities. Described is a robust direct catalytic asymmetric aldol reaction of α‐sulfanyl 7‐azaindolinylamide, thus affording both aromatic and aliphatic β‐hydroxy amides with high ee values. The design of this transformation features a cooperative interplay of a soft and a hard Lewis acid, which together facilitate the challenging chemoselective enolization by a hard Brønsted base. 相似文献
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A highly efficient catalytic system composed of a simple and commercially available chiral primary diamine (1R,2R)-cyclohexane-1,2-diamine(6) and trifluoroacetic acid (TFA) was employed for asymmetric Aldol reaction in em-PrOH at room temperature. A loading of 10%(molar fraction) catalyst 6 with TFA as a cocatalyst could catalyze the Aldol reactions of various ketones or aldehydes with a series of aromatic aldehydes, furnishing Aldol pro- ducts in moderate to high yields(up to >99%) with enantioselectivities of up to >99% and diastereoselectivities of up to 99:1. 相似文献
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Jarno Riefer Ludwig Zapf Dr. Raphael Wirthensohn Dr. Philipp T. Hennig Dr. Tatjana Ribbeck Dr. Jan A. P. Sprenger Dr. Nikolai V. Ignat'ev Prof. Dr. Maik Finze 《European journal of organic chemistry》2023,26(17):e202300031
Cyanoborane adducts of the Lewis acids B(CN)3, BF(CN)2, and BH(CN)2 with pyridine and 4-cyanopyridine have been obtained in high yields. The syntheses were accomplished by oxidation of the readily available potassium salts of the cyano(hydrido)borate anions [BH(CN)3]− ( MHB ), [BFH(CN)2]− ( FHB ), and [BH2(CN)2]− ( DHB ) with bromine in the presence of the respective pyridine derivative C5H5N or 4-CN-C5H4N as starting material. All six cyanoborane adducts have been characterized by NMR and vibrational spectroscopy, elemental analysis, and single-crystal X-ray diffraction. The reduction of the cyanoborane adducts has been investigated by cyclic voltammetry and the Lewis acidity of the different cyanoboranes has been assessed using the Gutmann-Beckett method. Selected experimental data and trends are compared to theoretical ones, for example fluoride ion affinities (FIAs). 相似文献
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Timoshkin A. Yu. Sevast'yanova T. N. Davydova E. I. Suvorov A. V. Schaefer H. F. 《Russian Journal of General Chemistry》2003,73(5):765-775
The structural and thermodynamic characteristics of SiX4·Py and SiX4·2Py adducts (X = H, F, Cl, Br) were calculated by ab initio and DFT methods (RHF and B3LYP). The resulting data were used to estimate for the first time the enthalpies of sublimation of trans-SiX4·2Py complexes. The distortion energies of the donor and acceptor fragments and the energies of the Si-N bonds in the 1:1 and 1:2 halide complexes were calculated. The high distortion energy makes thermodynamically unfavorable equatorial monopyridine adducts with Si-N bond energies of 150-200 kJ/mol. In trans 1:2 complexes, pyridine acts as a weaker donor than ammonia with respect to silicon tetrahalides. 相似文献
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