1009-14-9Relevant articles and documents
Palladium on carbon-catalyzed Α-alkylation of ketones with alcohols as electrophiles: Scope and mechanism
Bennedsen, Niklas R.,Mortensen, Rasmus L.,Kramer, S?ren,Kegn?s, S?ren
, p. 153 - 160 (2019)
The α-alkylation of ketones with alcohols represents a green strategy for the formation of crucial carbon–carbon bonds since it only produces water as byproduct. In terms of reaction mechanism, the evidence for homogeneous catalysis supports a catalytic hydrogen-borrowing pathway; however, the reaction mechanism has not been investigated for heterogeneous Pd/C catalysts. Here, we report an improved method for α-alkylation of ketones with alcohols using commercially available Pd/C, ubiquitous in organic synthesis labs, as catalyst. The reaction conditions are mild compared to state-of-the-art for both homo- and heterogeneous catalysts, and the developed conditions produces quantitative yields for most ketones and alcohols. A hot filtration experiment and recycling of the catalyst supports the heterogeneous nature of catalysis. Importantly, the reaction mechanism is studied for the first time by a combination of stoichiometric experiments and kinetic analyses by in-situ IR (React-IR).
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Pittman,C.U.,Hanes,R.M.
, p. 1194 - 1197 (1977)
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Reaction of Lithium Dialkylcuprates with S-2-Pyridiyl Thioates in the Presence of Oxygen. A Carboxylic Ester Synthesis
Kim, Sunggak,Lee, Jae In,Chung, Bong Young
, p. 1231 - 1232 (1981)
Reaction of lithium dialkylcuprates with S-2-pyridyl thioates in the presence of oxygen affords carboxylic esters in high yields, whereas under nitrogen it affords ketones.
New Heterocuprates with Greatly Improved Thermal Stability
Bertz, Steven H.,Dabbagh, Gary,Villacorta, G. M.
, p. 5824 - 5826 (1982)
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Ready Coupling of Acid Chlorides with Tetra-alkyl-lead Derivatives Catalysed by Palladium
Yamada, Jun-ichi,Yamamoto, Yoshinori
, p. 1302 - 1303 (1987)
Palladium-catalysed coupling of acid chlorides with tetra-alkyl-lead derivatives gives the corresponding ketones in high yields under mild conditions.
Palladium-Catalyzed Cross-Coupling Reactions of Carboxylic Anhydrides with Organozinc Reagents
Wang, Donghui,Zhang, Zhaoguo
, p. 4645 - 4648 (2003)
(Matrix presented) Negishi-type cross-coupling reaction was effected by employing organozincs and anhydrides or mixed anhydrides that formed in situ from sodium salts of the corresponding acids and ethyl chloroformate under the catalysis of palladium(0). A general method for preparing symmetrical/ unsymmetrical ketones was developed.
ANWENDUNG NICHTSTABILISIERTER EISEN(II)-ALKYLE ALS HOCHSELEKTIVE NUCLEOPHILE ALKYLIERUNGSREAGENZIEN
Kauffmann, Thomas,Laarmann, Barbara,Menges, Detlef,Voss, Karl-Uwe,Wingbermuehle, Dorothea
, p. 507 - 510 (1990)
Nonstabilized Fe(II) alkyls (RFeCl, R2Fe, R3FeM, R4FeM2; R=Me, n-Bu, M=Li, MgBr) are readily accessible in solution (THF, Et2O, CH2Cl2) by reaction of MeLi, MeMgBr, n-BuLi or n-BuMgBr, respectively, with FeCl2 at -78 to -50 deg C.The needed FeCl2 can be made by in-situ-reduction with RLi or RMgBr.For checking the transmetallation process the "β-bromostyrene-ketone-test" is especially favorable in case of the methyl derivatives.The prepared Fe compounds are alkylating reagents of high selectivity.
Nickel N-heterocyclic carbene-catalyzed cross-coupling reaction of aryl aldehydes with organozinc reagents to produce aryl ketones
Jin, Cheng,Gu, Lijun,Yuan, Minglong
, p. 4341 - 4345 (2015)
The transformation of aromatic aldehydes into aryl ketones by nickel-catalyzed cross-coupling has been developed. This transformation represents an efficient and attractive synthetic utilization of organozinc reagents. The reaction provides a mild, practical method toward the synthesis of aryl ketones which are versatile intermediates and building blocks in organic synthesis.
Alcohols for the α-alkylation of methyl ketones and indirect aza-wittig reaction promoted by nickel nanoparticles
Alonso, Francisco,Riente, Paola,Yus, Miguel
, p. 4908 - 4914 (2008)
Nickel nanoparticles have been found to activate primary alcohols used for the α-alkylation of ketones or in indirect aza-Wittig reactions. These processes involve hydrogen transfer from the alcohol to the intermediate α,β-unsaturated ketone or imine, respectively. All these reactions are carried out in the absence of any ligand, hydrogen acceptor or base under mild reaction conditions. For the first time nickel is employed as a potential alternative to noble-metal-based catalysts in both reactions. A reaction mechanism is proposed on the basis of some deuteration experiments. Wiley-VCH Verlag GmbH & Co. KGaA, 2008.
Regioselective ring-opening of cyclopropyl ketones with organometallic reagents
Ichiyanagi, Tsuyoshi,Kuniyama, Satoru,Shimizu, Makoto,Fujisawa, Tamotsu
, p. 1149 - 1150 (1997)
Regioselective ring-opening reaction of cyclopropyl ketones was conducted successfully, in which the reaction of cyclopropyl phenyl ketone with trimethylaluminum catalyzed by nickel acetyl-acetonate gave the ring-opening product in up to 76% yield.
Chemiluminescence of Imino-1,2-dioxetan Formed from Ketenimine and Singlet Oxygen
Ito, Yoshikatsu,Yokoya, Hiroaki,Kyono, Kazuaki,Yamamura, Soichiro,Yamada, Yutaka,Matsuura, Teruo
, p. 898 - 900 (1980)
The chemiluminescent properties of several imino-1,2-dioxetans prepared by the photosensitized oxygenation of ketenimines at -78 degC, indicate that the energy level of the transition state for their decomposition to the corresponding ketones and isocyanates is low and that the decomposition proceeds via a biradical mechanism.
Suzuki-Miyaura coupling of simple ketones via activation of unstrained carbon-carbon bonds
Xia, Ying,Wang, Jianchun,Dong, Guangbin
, p. 5347 - 5351 (2018)
Here, we describe that simple ketones can be efficiently employed as electrophiles in Suzuki-Miyaura coupling reactions via catalytic activation of unstrained C-C bonds. A range of common ketones, such as cyclopentanones, acetophenones, acetone and 1-indanones, could be directly coupled with various arylboronates in high site-selectivity, which offers a distinct entry to more functionalized aromatic ketones. Preliminary mechanistic study suggests that the ketone α-C-C bond was cleaved via oxidative addition.
Nickel catalyzed cross-coupling of modified alkyl and alkenyl Grignard reagents with aryl- and heteroaryl nitriles: Activation of the C-CN bond
Miller, Joseph A.,Dankwardt, John W.
, p. 1907 - 1910 (2003)
The nickel catalyzed cross-coupling of alkyl and alkenyl Grignard reagents with aryl nitrile derivatives affords good yields of the corresponding aryl alkanes or aryl alkenes via activation of the C-CN bond. To prevent direct addition of the nucleophile to the nitrile group, the reactivity of the Grignard reagent was modulated by reaction with either LiOt-Bu or PhSLi prior to cross-coupling. The optimum catalyst was determined to be NiCl2(PMe3)2, which is a convenient air stable commercially available complex.
A Palladium-Catalyzed Synthesis of Ketones from Acid Chlorides and Organozinc Compounds
Grey, Roger A.
, p. 2288 - 2289 (1984)
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Oxidative Nucleophilic Addition of Organovanadium Reagents to Aldehydes with Formation of Ketones
Hirao, Toshikazu,Misu, Daisuke,Agawa, Toshio
, p. 7179 - 7181 (1985)
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Nucleophilic properties of butyllithium versus free carboxylic acids
Einhorn,Einhorn,Luche
, p. 2771 - 2774 (1991)
In opposition to the generally accepted idea, butyl lithium is not only a deprotonating agent for free carboxylic acids, but can also act as a nucleophile on the carbon oxygen double bond.
H2-Generation from Alcohols by the MOF-Based Noble Metal-Free Photocatalyst Ni/CdS/TiO2@MIL-101
Tilgner, Dominic,Klarner, Mara,Hammon, Sebastian,Friedrich, Martin,Verch, Andreas,De Jonge, Niels,Kümmel, Stephan,Kempe, Rhett
, p. 842 - 847 (2019)
The synthesis of important classes of chemical compounds from alcohols helps to conserve Earth's fossil carbon resources, since alcohols can be obtained from indigestible and abundantly available biomass. The utilisation of visible light for the activation of alcohols permits alcohol-based C-N and C-C bond formation under mild conditions inaccessible with thermally operating hydrogen liberation catalysts. Herein, we report on a noble metal-free photocatalyst able to split alcohols into hydrogen and carbonyl compounds under inert gas atmosphere without the requirement of electron donors, additives, or aqueous reaction media. The reusable photocatalyst mediates C-N multiple bond formation using the oxidation of alcohols and subsequent coupling with amines. The photocatalyst consists of a CdS/TiO2 heterojunction decorated with co-catalytic Ni nanoparticles and is prepared on size-optimised colloidal metal-organic framework (MOF) crystallites.
Godet,Pereyre
, p. C1 (1974)
Synthesis of Functionalized Ketones from Acid Chlorides and Organolithiums by Extremely Fast Micromixing
Nagaki, Aiichiro,Sasatsuki, Kengo,Ishiuchi, Satoshi,Miuchi, Nobuyuki,Takumi, Masahiro,Yoshida, Jun-ichi
, p. 4946 - 4950 (2019)
Synthesis of ketones containing various functional groups from acid chlorides bearing electrophilic functional groups and functionalized organolithiums was achieved using a flow microreactor system. Extremely fast mixing is important for high chemoselectivity.
Reactivities of mixed organozinc and mixed organocopper reagents: 1 - Solvent controlled organic group transfer from mixed diorganozincs
Erdik, Ender,Pekel, ?zgen ?mür
, p. 338 - 342 (2008)
The selectivity of organyl group transfer in the copper catalyzed benzoylation of n-butyl phenylzinc in THF depends on N-, O- or P-donor cosolvents and additives as well as copper salts and Lewis acids. In THF:NMP (3:1) and in THF:diglyme (2:1), n-butyl group/ phenyl group transfer ratio is 9:1 whereas only n-butyl group transfer is observed in THF:n-Bu3P (1 equiv.) and only phenyl group transfer is observed in THF:TMEDA (2:1).
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Richey,H.G. et al.
, p. 2187 - 2190 (1971)
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Preparation of ketones via the palladium-catalyzed cross-coupling of acid chlorides with trialkylboranes
Kabalka, George W.,Malladi, Rama R.,Tejedor, David,Kelley, Shane
, p. 999 - 1001 (2000)
Trialkylboranes react with acid chlorides in the presence of palladium to generate alkyl and aryl ketones in good yields. (C) 2000 Elsevier Science Ltd.
Simple one pot synthesis of ketone from carboxylic acid using DCC as an activator
Mekonnen, Habtamu Gelaw,Jana, Samaresh
, p. 1382 - 1384 (2019)
Simple one pot procedure for the conversion of carboxylic acid to ketone is described. Various carboxylic acids were converted to the corresponding ketones in excellent manner in presence of N,N′-dicyclohexylcarbodiimide (DCC) and organometallic reagents. Aromatic, heteroaromatic and aliphatic acids were converted to the corresponding ketones smoothly under the optimum conditions using organolithium reagents. In this process, desired products have been isolated from the crude reaction mixtures in moderate yields during the purification process.
Palladium-catalyzed carboacylation of alkenes by using acylchromates as acyl donors
Yamane, Motoki,Kubota, Yuko,Narasaka, Koichi
, p. 331 - 340 (2005)
Palladium-catalyzed arylacylation of alkenes proceeds by employing acylchromates as acyl donors. When active alkenes such as norbornene and methoxyallene are treated with an aryl iodide, an acylchromate, and a catalytic amount of Pd(OAc)2/2P(o-Tol)3, arylacylation of these alkenes proceeds at room temperature. From aryl iodides having an intramolecular alkene moiety, cyclization-acylation products are obtained via intramolecular arylpalladation followed by acylation with acylchromates.
Crystal structures and photoreactivity of transand cis-valerophenone diperoxides
Takahashi, Hiroki,Ito, Yoshikatsu
, p. 441 - 449 (2012)
The crystal structures of valerophenone diperoxides trans-1 and cis-1 were elucidated by X-ray crystallographic analysis. The 1,2,4,5-tetraoxane rings of both compounds adopt chair conformations. Intermolecular CH...O hydrogen bond, π-π, and CH/π interactions exist in cis-1, whereas only CH/π interactions exist in trans-1. In the asymmetric unit of the crystal, a half molecule exists for trans-1, while one molecule for cis-1 which shows wholemolecule disorder. Solid-state photolysis (at 254 nm) or solution-state thermolysis (at 150 °C) of trans-1 and cis-1 produced valerophenone (2) and butyl benzoate (3). Rationalization of the solid-state photoreactivity of the diperoxides by their crystal structures was attempted. Springer Science+Business Media, LLC 2011.
Contra-Thermodynamic Positional Isomerization of Olefins
Zhao, Kuo,Knowles, Robert R.
supporting information, p. 137 - 144 (2022/01/19)
A light-driven method for the contra-thermodynamic positional isomerization of olefins is described. In this work, stepwise PCET activation of a more substituted and more thermodynamically stable olefin substrate is mediated by an excited-state oxidant an
Nickel-Catalyzed Reductive Acylation of Carboxylic Acids with Alkyl Halides and N-Hydroxyphthalimide Esters Enabled by Electrochemical Process
Guo, Lin,Xia, Raymond Yang,Xia, Wujiong,Yang, Chao,Zhang, Haoxiang,Zhou, Xiao
supporting information, (2022/03/31)
A sustainable Ni-catalyzed reductive acylation reaction of carboxylic acids via an electrochemical pathway is presented, affording a variety of ketones as major products. The reaction proceeds at ambient temperature using unactivated alkyl halides and N-hydroxyphthalimide (NHP) esters as coupling partners, which exhibits several synthetic advantages, including mild conditions and convenience of amplification (58% yield for 6 mmol scale reaction). (Figure presented.).
Ruthenium-on-Carbon-Catalyzed Facile Solvent-Free Oxidation of Alcohols: Efficient Progress under Solid-Solid (Liquid)-Gas Conditions
Park, Kwihwan,Jiang, Jing,Yamada, Tsuyoshi,Sajiki, Hironao
, p. 1200 - 1205 (2021/12/29)
A protocol for the ruthenium-on-carbon (Ru/C)-catalyzed solvent-free oxidation of alcohols, which proceeds efficiently under solid-solid (liquid)-gas conditions, was developed. Various primary and secondary alcohols were transformed to corresponding aldehydes and ketones in moderate to excellent isolated yields by simply stirring in the presence of 10% Ru/C under air or oxygen conditions. The solvent-free oxidation reactions proceeded efficiently regardless of the solid or liquid state of the substrates and reagents and could be applied to gram-scale synthesis without loss of the reaction efficiency. Furthermore, the catalytic activity of Ru/C was maintained after five reuse cycles.
