925-78-0Relevant academic research and scientific papers
METHOD FOR CONVERTING HYDROXYL GROUP OF ALCOHOL
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Paragraph 0493-0494, (2021/02/19)
The present invention relates to: a method for converting a hydroxyl group of an alcohol; and a catalyst which makes the method possible. A method for converting a hydroxyl group of an alcohol according to the present invention is characterized by producing a compound represented by CH(R1)(R2)Nu (wherein R1, R2 and Nu are as defined below) by reacting an alcohol represented by CH(R1)(R2)OH (wherein each of R1 and R2 represents a hydrogen atom, an optionally substituted alkyl group, or the like) and a compound having an active proton, which is represented by H-Nu (wherein Nu represents a group represented by —CHX1-EWG1 or —NR3R4; X1 represents a hydrogen atom or the like; EWG1 represents an electron-withdrawing group; and each of R3 and R4 represents a hydrogen atom, an optionally substituted alkyl group, or the like), with each other in the presence of a complex of a group 7-11 metal of the periodic table and at least one solid base that is selected from the group consisting of layered double hydroxides, composite oxides and calcium hydroxide.
Chelation-Assisted C-H and C-C Bond Activation of Allylic Alcohols by a Rh(I) Catalyst under Microwave Irradiation
Lee, Chang-Hee,Jun, Chul-Ho
, p. 736 - 741 (2017/11/27)
Chelation-assisted Rh(I)-catalyzed ketone synthesis from allylic alcohols and alkenes through C-H and C-C bond activations under microwave irradiation was developed. Aldimine is formed via olefin isomerization of allyl alcohol under Rh(I) catalysis and condensation with 2-amino-3-picoline, followed by continuous C-H and C-C bond activations to produce a dialkyl ketone. The addition of piperidine accelerates the reaction rate by promoting aldimine formation under microwave conditions.
C -Methylation of Alcohols, Ketones, and Indoles with Methanol Using Heterogeneous Platinum Catalysts
Siddiki, S. M. A. Hakim,Touchy, Abeda S.,Jamil, Md. A. R.,Toyao, Takashi,Shimizu, Ken-Ichi
, p. 3091 - 3103 (2018/04/14)
A versatile, selective, and recyclable heterogeneous catalytic method for the methylation of C-H bonds in alcohols, ketones, and indoles with methanol under oxidant-free conditions using a Pt-loaded carbon (Pt/C) catalyst in the presence of NaOH is reported. This catalytic system is effective for various methylation reactions: (1) the β-methylation of primary alcohols, including aryl, aliphatic, and heterocyclic alcohols, (2) the α-methylation of ketones, and (3) the selective C3-methylation of indoles. The reactions are driven by a borrowing-hydrogen mechanism. The reaction begins with the dehydrogenation of the alcohol(s) to afford aldehydes, which subsequently undergo a condensation reaction with the nucleophile (aldehyde, ketone, or indole), followed by hydrogenation of the condensation product by Pt-H species to yield the desired product. In all of the methylation reactions explored in this study, the Pt/C catalyst exhibits a significantly higher turnover number than other previously reported homogeneous catalytic systems. Moreover, it is demonstrated that the high catalytic activity of Pt can be rationalized in terms of the adsorption energy of hydrogen on the metal surface, as revealed by density functional theory calculations on different metal surfaces.
Photocatalytic Transfer Hydrogenolysis of Allylic Alcohols on Pd/TiO2: A Shortcut to (S)-(+)-Lavandulol
Takada, Yuki,Caner, Joaquim,Kaliyamoorthy, Selvam,Naka, Hiroshi,Saito, Susumu
supporting information, p. 18025 - 18032 (2017/12/08)
We report herein a regio- and stereoselective photocatalytic hydrogenolysis of allylic alcohols to form unsaturated hydrocarbons employing a palladium(II)-loaded titanium oxide; the reaction proceeds at room temperature under light irradiation without stoichiometric generation of salt wastes. Olefin and saturated alcohol moieties tolerated the reaction conditions. Hydrogen atoms were selectively incorporated into less sterically congested carbons of the allylic functionalities. This protocol allowed a short-step synthesis of (S)-(+)-lavandulol from (R)-(?)-carvone by avoiding otherwise necessary protection/deprotection steps.
Regioselective Isomerization of 2,3-Disubstituted Epoxides to Ketones: An Alternative to the Wacker Oxidation of Internal Alkenes
Lamb, Jessica R.,Mulzer, Michael,Lapointe, Anne M.,Coates, Geoffrey W.
supporting information, p. 15049 - 15054 (2015/12/08)
We report an alternative pathway to the Wacker oxidation of internal olefins involving epoxidation of trans-alkenes followed by a mild and highly regioselective isomerization to give the major ketone isomers in 66-98% yield. Preliminary kinetics and isotope labeling studies suggest epoxide ring opening as the turnover limiting step in our proposed mechanism. A similar catalytic system was applied to the kinetic resolution of select trans-epoxides to give synthetically useful selectivity factors of 17-23 for benzyl-substituted substrates.
Simple and clean synthesis of ketones from internal olefins using PdCl 2/N,N-dimethylacetamide catalyst system
Mitsudome, Takato,Yoshida, Syuhei,Tsubomoto, Yamato,Mizugaki, Tomoo,Jitsukawa, Koichiro,Kaneda, Kiyotomi
supporting information, p. 1596 - 1598 (2013/03/14)
A simple catalytic system consisting of PdCl2 and N,N-dimethylacetamide enabled clean and selective synthesis of ketones from internal olefins using molecular oxygen. Various functionalized internal olefins were directly and regioselectively oxidized; C atoms of CC bonds far from substituted moieties were preferably oxidized.
Air-stable, nitrile-ligated (cyclopentadienone)iron dicarbonyl compounds as transfer reduction and oxidation catalysts
Plank, Taylor N.,Drake, Jessica L.,Kim, Daniel K.,Funk, Timothy W.
supporting information; experimental part, p. 597 - 601 (2012/05/04)
A series of air-stable, nitrile-ligated (cyclopentadienone)iron dicarbonyl compounds was synthesized and their activities as catalysts in the transfer reduction of acetophenone were explored. While all were active catalysts, the acetonitrile adduct was chosen for further study and was found to be active in the transfer reduction of aldehydes and ketones and in the Oppenauer-type oxidation of secondary alcohols. The acetonitrile catalyst exhibited activities similar to those of an analogous air-sensitive iron hydride, but unlike the iron hydride it was unreactive in carbonyl reductions using hydrogen gas. Copyright
Double hydroacylation reactions of acyclic and cyclic α,β- unsaturated aldehydes
Cha, Kyung-Mi,Lee, Hyejeong,Park, Jung-Woo,Lee, Yura,Jo, Eun-Ae,Jun, Chul-Ho
supporting information; experimental part, p. 1926 - 1930 (2011/10/17)
Double or quits? double hydroacylation reactions of acyclic and cyclic α,β-unsaturated aldehydes with olefins afford ketone and diketone products, respectively. Enantiomers are formed whose absolute configurations are controlled by the order of alkene addition.
New platinum-catalysed dihydroalkoxylation of allenes
Munoz, Maria Paz,De La Torre, Maria C.,Sierra, Miguel A.
supporting information; experimental part, p. 2189 - 2194 (2010/11/04)
A new platinum-catalysed dihydroalkoxylation of alienes is described to give aliphatic acetals by an unexpected attack of two molecules of methanol to the terminal carbon of the aliene moiety. Deuteration experiments suggest an unprecedented formal 1,3-dipolar addition of methanol to a zwitterionic platinum carbene as the key step. The first platinum-catalysed intermolecular carbonbased nucleophile addition to alienes is also reported.
Air-stable iron catalyst for the Oppenauer-type oxidation of alcohols
Moyer, Sara A.,Funk, Timothy W.
experimental part, p. 5430 - 5433 (2010/10/20)
An alcohol oxidation process using an air-stable iron tricarbonyl compound structurally similar to Shvo's diruthenium bridging hydride was developed. Secondary benzylic and allylic alcohols are oxidized in high yields, and evidence for an Oppenauer-type mechanism is presented.
