112-40-3Relevant articles and documents
Solvent-dependent substrate reduction by {Sm[N(SiMe3)2]2(THF)2}. An alternative approach for accelerating the rate of substrate reduction by Sm(II)
Chciuk, Tesia V.,Hilmersson, G?ran,Flowers, Robert A.
, p. 9441 - 9443 (2014)
The impact of solvent on electron transfer from Sm(II) to substrates was measured by determining the rate of reduction of 1-bromo-, 1-chlorododecane, and 3-pentanone in THF and hexanes using the highly soluble reductant {Sm[N(SiMe3)2]2(THF)2}. Rates were found to be 3 orders of magnitude faster in hexanes than THF, and reductions of alkyl halides were inverse first order in THF. These findings show the solvent milieu signifi cantly impacts the rate of substrate reduction, a consideration that may prove useful in synthesis. (Chemical Equation Presented).
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Mukaiyama,T. et al.
, p. 23 - 24 (1969)
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Prominent hydrogenation catalysis of a PVP-stabilized Au34 superatom provided by doping a single Rh atom
Hasegawa, Shingo,Takano, Shinjiro,Yamazoe, Seiji,Tsukuda, Tatsuya
, p. 5915 - 5918 (2018)
A single rhodium atom was precisely doped into a gold cluster Au34 stabilized by poly(N-vinyl-2-pyrrolidone) (Au:PVP) as revealed by mass spectrometry. The Rh-atom-doped Au:PVP exhibited remarkable catalytic activity for hydrogenation reactions of olefins, which was much higher than that of recently reported Pd-atom-doped Au:PVP.
Additive and Solvent Effects on SmI2 Reductions: The Effects of Water and DMPU
Hasegawa, Eietsu,Curran, Dennis P.
, p. 5008 - 5010 (1993)
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Hutchins et al.
, p. 1088 (1978)
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Conversion of biomass-derived fatty acids and derivatives into hydrocarbons using a metal-free hydrodeoxygenation process
Li, Xing-Yu,Shang, Rui,Fu, Ming-Chen,Fu, Yao
, p. 2790 - 2793 (2015)
A metal-free hydrodeoxygenation process was developed for the production of hydrocarbons from biomass-derived fatty acids and derivatives. Biomass-derived fatty acids and derivatives were converted to alkanes and alkenes under mild reaction conditions. Furthermore, this catalytic system can also be applied to convert real biomass with satisfactory results.
Polycyclic aromatic compounds-mediated electrochemical reduction of alkyl mesylates
Senboku, Hisanori,Takahashi, Megumi,Fukuhara, Tsuyoshi,Hara, Shoji
, p. 228 - 229 (2007)
Electrochemical reduction of alkyl mesylates was successfully carried out by using an undivided cell equipped with a Pt cathode and an Mg anode in the presence of biphenyl and t-BuOH. The reaction could proceed efficiently under mild conditions to give the corresponding alkanes in moderate to good yields. This procedure could also be applicable to chemoselective reduction of mesylates having functional groups such as epoxide, olefin, acetal, hydroxy, or cyano groups. Copyright
Enhanced Reducing Ability by the Combination of SmI2 and Sm Metal in the Reduction of Alkyl Halides
Ogawa, Akiya,Nanke, Taizoh,Takami, Noriaki,Sumino, Yukihito,Ryu, Ilhyong,Sonoda, Noboru
, p. 379 - 380 (1994)
Reduction of alkyl bromides and iodides easily takes place under mild conditions by the use of a reaction system combining SmI2 with Sm metal.The reducing ability of this Sm/SmI2 mixed reagent is superior to that of SmI2 or Sm metal used independently.
N-Ethylpiperidine Hypophosphite Mediated Intermolecular Radical Carbon-Carbon Bond Forming Reaction in Water
Jang, Doo Ok,Cho, Dae Hyan
, p. 1523 - 1525 (2002)
N-Ethylpiperidine hypophosphite mediated radical addition reactions to electron deficient alkenes in aqueous media have been developed. The reactions afford high isolated yields of addition products without using a large excess of alkenes.
Thermoregulated phase-transfer rhodium nanoparticle catalyst for hydrogenation in an aqueous/organic biphasic system
Li, Kaoxue,Wang, Yanhua,Jiang, Jingyang,Jin, Zilin
, p. 542 - 546 (2010)
A simple, effective and reversible aqueous/organic phase-transfer method for rhodium nanoparticles was developed on the basis of the cloud point (Cp) of thermoregulated ligand. The rhodium nanoparticles stabilized by thermoregulated ligand Ph2P(CH2CH2O)nCH3 (n = 16) could transfer from aqueous phase to 1-butanol phase and vice versa by means of changing temperature. This thermoregulated phase-transfer rhodium nanoparticle catalyst evaluated in the hydrogenation of olefins in an aqueous/1-butanol biphasic system exhibited high activity and stability.
The Reductive Coupling of Organic Halide Using Hydrazine and a Palladium Amalgam Catalyst. I. The Preparation of Biaryls
Nakajima, Riichiro,Shintani, Yuji,Hara, Tadashi
, p. 1767 - 1768 (1980)
Iodoarenes could be converted to the corresponding biaryls in high yields by use of a catalytic amount of a palladium amalgam in place of a palladium-calcium carbonate catalyst in Busch's reaction.The 2,3'-isomer content in the bitolyls obtained by the homo-coupling of o-iodotoluene was 15percent when palladium was used, while it was 1percent when a palladium amalgam was used, and the latter was re-usable.The present method is further applicable to some iodoalkanes.
CATALYTIC HYDROGENATION OF ALKYNES TO CIS-ALKENES ON A MODIFIED BORON-NICKEL CATALYST
Siimer, E. Kh.,Petrova, S. S.
, p. 2516 - 2518 (1991)
Hydrogenation of alkynes from decyne and dodecyne (C10-C12) with the triple bond at C3, C4, C5, and C6 led to the corresponding alkenes on a boron-nickel catalyst modified by a 1-phenyl-2,3-dimethyl-4-amino-5-pyrazolone (4-aminoantipyrene).The stereospecificity for formation of the cis-alkenes was 95-98percent.
Novel reducing properties of a series of lanthanoid metals in the presence of SmI2
Tomisaka, Yuri,Yoshimura, Aya,Nomoto, Akihiro,Sonoda, Motohiro,Ogawa, Akiya
, p. 43 - 48 (2013)
The reduction of dodecyl iodide, as model compound, with a series of lanthanoid (Ln) metals in the presence of catalytic amounts of samarium diiodide (SmI2) has been investigated in detail. The reducing activity of SmI2/Ln and the kinds of reduced products were found to be dependent on the individual Ln, but not on SmI2.
Synthetic radical reactions using dibutylchlorogermane and dibutylethoxygermane as radical mediators
Miura, Katsukiyo,Ootsuka, Kazunori,Hosomi, Akira
, p. 3151 - 3153 (2005)
In the presence of Et3B as radical initiator, dibutylchlorogermane (1a) and dibutylethoxygermane (1b) reacted with bromo- and iodoalkanes at room temperature to give the corresponding alkanes in high yields. Hydrogermane 1a was more reactive than 1b. However, 1b worked as a better radical mediator in intermolecular radical addition of haloalkanes to electron-deficient alkenes. Georg Thieme Verlag Stuttgart.
Expanding the scope of trialkylborane/water-mediated radical reactions
Medeiros, Matthew R.,Schacherer, Laura N.,Spiegel, David A.,Wood, John L.
, p. 4427 - 4429 (2007)
(Formula Presented) The dehalogenation of alkyl iodides, as well as the chemoselective deoxygenation of a secondary alcohol in the presence of various alkyl and aryl halides, can be accomplished employing a trialkylborane/air/water system.
Thiol-catalysed Radical-chain Reduction of Organic Halides by Hexabutylditin in the Presence of Malonic Acid
Kim, Kyoung-Mahn,Roberts, Brian P.
, p. 132 - 133 (1998)
In the presence of a thiol catalyst and a suitable initiator, a mixture of hexabutylditin and malonic acid brings about protodehalogenation of organic bromides and iodides by a radical-chain mechanism.
Hydrodeoxygenation of fatty acids and triglycerides by Pt-loaded Nb2O5catalysts
Kon, Kenichi,Onodera, Wataru,Takakusagi, Satoru,Shimizu, Ken-Ichi
, p. 3705 - 3712 (2014)
Platinum nanoparticles loaded onto various supports have been studied for the selective hydrogenation of lauric acid to n-dodecane. The activity depends on the support material and pre-reduction temperature. Pt/Nb2O5reduced at 300 °C gives the highest activity. Pt/Nb2O5shows higher activity than various Nb2O5-supported transition metals (Ir, Re, Ru, Pd, Cu, Ni). Under solvent-free conditions Pt/Nb2O5is effective for the hydrodeoxygenation of lauric, capric, palmitic, myristic, oleic, and stearic acids under 8 bar H2at 180-250 °C, which gives high yields (88-100%) of linear alkanes with the same chain length as the starting compound. Tristearin is also converted to give 93% yield of n-octadecane. Pt/Nb2O5shows more than 60 times higher turnover number (TON) than the previously reported catalysts for the hydrogenation of stearic acid to n-octadecane. Mechanistic study shows a consecutive reaction pathway in which lauric acid is hydrogenated to 1-dodecanol, which undergoes esterification with lauric acid as well as hydrogenation to n-dodecane. The ester undergoes hydrogenolysis to give the alcohol, which is hydrogenated to the alkane. Infrared (IR) study of acetic acid adsorption on Nb2O5indicates that Lewis acid-base interaction of Nb cation and carbonyl oxygen, which suggests a possible role of Nb2O5as an activation site of carbonyl groups during hydrodeoxygenation. This journal is
Co-Catalyzed Cross-Coupling Reaction of Alkyl Fluorides with Alkyl Grignard Reagents
Iwasaki, Takanori,Yamashita, Koji,Kuniyasu, Hitoshi,Kambe, Nobuaki
, p. 3691 - 3694 (2017)
The cross-coupling reaction of unactivated alkyl fluorides with alkyl Grignard reagents by a CoCl2/LiI/1,3-pentadiene catalytic system is described. The present reaction smoothly cleaved C-F bonds under mild conditions and achieved alkyl-alkyl cross-coupling even when sterically hindered tertiary alkyl Grignard reagents were employed. Since alkyl fluorides are inert toward many reagents and catalytic intermediates, the use of the present reaction enables a new multistep synthetic route to construct carbon frameworks by combining conventional transformations.
Wilkinson-type hydrogenation catalysts immobilized on zirconium phosphate nanoplatelets
Silbernagel, Rita,Díaz, Agustín,Steffensmeier, Eric,Clearfield, Abraham,Blümel, Janet
, p. 217 - 223 (2014)
Immobilized catalysts can be obtained by using a linker to bind a homogeneous catalyst to a solid support. Ideally, immobilized catalysts combine the advantages of homogeneous and heterogeneous catalysts. Porous supports such as silica result in optimal recyclability, however, the catalytic reactions are slowed down by pore diffusion. Here, non-porous zirconium phosphate nanoplatelets (ZrP) are used as support material to bridge the gap between homogeneous and immobilized catalysts. ZrP nanoplatelets provide sufficient outside surface area, while still being easily separable from the reaction mixtures. First, a phosphine linker containing an ethoxysilyl group, (EtO) 3Si(CH2)3PPh2 (1), is reacted with ZrP to give the phosphine-modified 1i. Addition of Wilkinson's catalyst ClRh(PPh3)3 to 1i gives, via ligand exchange, the immobilized catalyst 1i-Rh. In the absence of pore diffusion the catalytic hydrogenation of 1-dodecene using 1i-Rh proceeds with unprecedented speed and the catalyst can be recovered and recycled 15 times. In the course of the catalytic reaction the mononuclear species forms catalytically active Rh nanoparticles on the surface. Finally it is demonstrated that ClRh(PPh 3)3 can be bound to ZrP directly without linker. However, the catalytic activity of the resulting material ZrP-Rh does not quite match the favorable characteristics of 1i-Rh.
9,10-Dihydro-9,10-disilaanthracenes as a New Radical-based Reducing Agent: Importance of Transannular Interaction Between Silyl Radical and Silicon Atom
Oba, Makoto,Nishiyama, Kozaburo
, p. 1703 - 1704 (1994)
9,10-Dihydro-9,10-disilaanthracenes containing Si-H moieties at 9,10-positions are effective reducing agents in AIBN-initiated dehalogenation and deoxygenation reactions, in which a transannular interaction between silyl radical and silicon atom is considered important.
Lithium hydride containing complex reducing agent: A new and simple activation of commercial lithium hydride
Fort, Yves
, p. 6051 - 6054 (1995)
Commercially available lithium hydride, an essentially inert metal hydride, can be activated as a hydride source by in situ generated lithium alkoxide in the presence of a nickel salt. The obtained new reagent exhibited reducing properties versus alkyl or aryl halides, ketones, ethylenic or sulfurated compounds as well as coupling properties versus aryl halides when prepared in the presence of a ligand.
Palladium-catalyzed reduction of olefins with triethylsilane
Mirza-Aghayan, Maryam,Boukherroub, Rabah,Bolourtchian, Mohammad,Hosseini, Maryam
, p. 4579 - 4580 (2003)
The versatility of the palladium(II) chloride and triethylsilane system has been tested in the hydrogenation of 1-alkenes. The reduction of 1-alkenes was carried out in the presence of triethylsilane, ethanol and a catalytic amount of palladium(II) chloride, at room temperature. This facile and efficient method affords high yields for hydrogenation of unsaturated alkenes to the corresponding alkanes.
The Retro-Hydroformylation Reaction
Kusumoto, Shuhei,Tatsuki, Toshiumi,Nozaki, Kyoko
, p. 8458 - 8461 (2015)
Hydroformylation, a reaction that adds carbon monoxide and dihydrogen across an unsaturated carbon-carbon multiple bond, has been widely employed in the chemical industry since its discovery in 1938. In contrast, the reverse reaction, retro-hydroformylation, has seldom been studied. The retro-hydroformylation reaction of an aldehyde into an alkene and synthesis gas (a mixture of carbon monoxide and dihydrogen) in the presence of a cyclopentadienyl iridium catalyst is now reported. Aliphatic aldehydes were converted into the corresponding alkenes in up to 91 % yield with concomitant release of carbon monoxide and dihydrogen. Mechanistic control experiments indicated that the reaction proceeds by retro-hydroformylation and not by a sequential decarbonylation-dehydrogenation or dehydrogenation-decarbonylation process.
Acid-tolerant cyclodextrin-based ruthenium nanoparticles for the hydrogenation of unsaturated compounds in water
No?l, Sébastien,Bourbiaux, Dolorès,Tabary, Nicolas,Ponchel, Anne,Martel, Bernard,Monflier, Eric,Léger, Bastien
, p. 5982 - 5992 (2017)
A water-soluble β-cyclodextrin polymer synthesized by crosslinking β-cyclodextrin with epichlorohydrin and glycidyltrimethylammonium chloride allowed the stabilization of ruthenium nanoparticles not only in basic aqueous medium but also in acidic medium. The aqueous ruthenium colloidal suspensions obtained with this polymer were active as catalysts for the hydrogenation of a large variety of unsaturated compounds including aromatic or fatty acids. The recycling of this catalytic system was attested through ten consecutive runs without loss of stability and activity, demonstrating its robustness.
Phenylsilane: A convenient reagent for the radical dehalogenation of organic halides
Jang, Doo Ok
, p. 1023 - 1027 (1997)
Phenylsilane has been used for the reduction of alkyl and aryl halides. The method offers mild, neutral reaction conditions, easy work-up process, and high yields of the dehalogenated products.
Selective Alkyne Semi-Hydrogenation by PdCu Nanoparticles Immobilized on Stereocomplexed Poly(lactic acid)
Capozzoli, Laura,Evangelisti, Claudio,Frediani, Marco,Mohammadi Dehcheshmeh, Iman,Najafi Moghadam, Peyman,Oberhauser, Werner,Poggini, Lorenzo
, (2022/03/01)
Polymer-supported PdCu alloy nanoparticles with a palladium to copper atom ratio of 1 have been synthesized upon: (i) Coordination of palladium/copper acetate to 2,2’-bipyridine-end functionalized poly(lactic acid) (PLA); (ii) Stereocomplexation of PLA-based macrocomplexes of opposite stereochemistry, and (iii) metal reduction with hydrogen. The obtained supported PdCu nanoparticles were successfully applied in the semi-hydrogenation of industrially important alkynols, such as 3-hexyn-1-ol and 2-butyne-1,4-diol leading to the corresponding cis-alkenol in high selectivity (98 %) under mild reaction conditions (i. e. ethanol, T (25 °C), p(H2)=3 bar) in the absence of any further additive. From a comparison of the catalytic performance of supported PdCu nanoparticles with those of Pd and Cu, located in the same chemical environment, emerged a clear alloy effect (i. e. high chemoselectivity for the alkene at high alkyne conversion). Recycling experiments conducted with the PdCu-based catalyst proved the stability of the catalyst with time, even by its recovering in air atmosphere.
Visible light-driven Giese reaction with alkyl tosylates catalysed by nucleophilic cobalt
Komeyama, Kimihiro,Michiyuki, Takuya,Teshima, Yoshikazu,Osaka, Itaru
, p. 3539 - 3546 (2021/02/03)
The scope of the Giese reaction is expanded using readily available alkyl tosylates as substrates and nucleophilic cobalt(i) catalysts under visible-light irradiation. The reaction proceeds preferentially with less bulky primary alkyl tosylates. This unique reactivity enables the regio-selective Giese reaction of polyol derivatives.
Microwave-Assisted Nickel-Catalyzed Rapid Reductive Coupling of Ethyl 3-iodopropionate to Adipic Acid
Zhang, Linfeng,Zheng, Jing,Zou, Wenya,Shu, Yongqi,Yang, Weiran
, p. 2339 - 2345 (2021/01/04)
Abstract: 3-iodopropionic acid (3-IPA) can be efficiently synthesized from the glycerol derivative glyceric acid (GA), which is a potential biomaterial-based platform molecule. In this report, ethyl 3-iodopropionate was rapidly dimerized to diethyl adipate in a microwave reactor using NiCl2·6H2O as a catalyst, co-catalyzed by Mn and the 1, 10-Phenanthroline monohydrate ligand. Under the optimum reaction conditions, diethyl adipate can be obtained with 84% yield at 90?°C in just 5?min. Diethyl adipate was hydrolyzed to obtain the adipic acid (AA) in 89% yield with an acid catalyst. AA is an important chemical and a monomer for producing a wide range of high-performance polymeric substances. This rapid coupling method is also applicable to other alkyl halides. Graphic Abstract: [Figure not available: see fulltext.]