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).
A simple synthesis of ketone from carboxylic acid using tosyl chloride as an activator
Jana, Samaresh,Sahoo, Debasis,Sarkar, Sohini
, (2019)
An effective process for the conversion of carboxylic acid to ketone has been discovered. In this process, carboxylic acid has been activated using p-toluene sulphonyl group. Under the optimized condition, aromatic, aliphatic heteroaromatic carboxylic acids have been proved to be good substrates for this methodology. The byproduct of this reaction can be removed very easily during work up process. Also, one equivalent of organometallic reagent is sufficient to complete this transformation.
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.
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.
A FACILE PREPARATION OF TELLUROL ESTERS FROM PHENYLTELLUROTRIMETHYLSIANE AND ACYL CHLORIDES
Sasaki, Kazuaki,Aso, Yoshio,Otsubo, Tetsuo,Ogura, Fumio
, p. 977 - 978 (1986)
Phenyltellurotrimethylsilane cleanly reacted with acyl chloride, giving tellurol ester in an excellent yield.The high rectivity of tellurol ester toward lithium organocuprate was demonstrated.
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.
A Palladium Bipyridyl Complex Grafted onto Nanosized MCM-41 as a Heterogeneous Catalyst for Negishi Coupling
Wu, Wei-Yi,Lin, Tze-Chiao,Takahashi, Tamotsu,Tsai, Fu-Yu,Mou, Chung-Yuan
, p. 1011 - 1019 (2013)
The Negishi coupling of aryl bromides or acyl chlorides with organozinc chlorides catalyzed by a palladium bipyridyl complex anchored on nanosized mobile crystalline material 41 (MCM-41) were investigated. The reactions proceeded smoothly with a very low catalyst loading in THF at 70°C for electron-deficient aryl bromides, which gave good to high yields of the Negishi coupling products. However, reactions in toluene at 110°C were required if electron-rich aryl bromides were employed. For acyl chlorides, the reactions could be performed in THF at 50°C and the corresponding ketones and ynones were obtained in high yields. After centrifugation, it was possible to easily recover the supported catalyst from the reaction mixture, and this could be reused several times without any retreatment or regeneration with only a slight decrease in activity.
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.
Polystyrene resins containing 1,3-propanedithiol functions for solid-phase organic syntheses
Bertini, Vincenzo,Pocci, Marco,Lucchesini, Francesco,Alfei, Silvana,De Munno, Angela
, p. 864 - 866 (2003)
A completely odourless reliable synthesis of styrenic resins containing 1,3-propanedithiol functions able to form 1,3-dithiane derivatives with carbonyl compounds and back up the chemistry of thioacetals and thioketals is reported. The degree of functionalisation of the resin can be easily determined through the composition of the copolymerising mixture and confirmed by titration. The resins show good accessibility to various reagents and are effective for solid-phase synthesis being exploitable in the field of combinatorial chemistry.
