143-08-8Relevant academic research and scientific papers
Alcoholysis and carbonyl hydrosilylation reactions using a polymer- supported trialkylsilane
Hu, Yonghan,Porco Jr., John A.
, p. 2711 - 2714 (1998)
Polystyrene-diethylsilane (PS-DES) resin may be reacted with alcohols (alcoholysis) and carbonyl compounds (hydrosilylation) in 1-methyl-2- pyrrolidinone (NMP) using Wilkinson's catalyst (RhCl(PPh3)3) to afford the corresponding resin-bound silyl ethers. The silyl ethers formed were effectively cleaved using HF/pyridine solution in THF. Methoxytrimethylsilane was employed to scavenge excess HF from product solutions.
Pentacoordinate Hydridosiliconates with Bidentate Ligands Derived from Hexafluorocumyl Alcohol. Characterization and Reduction of Carbonyl Compounds
Kira, Mitsuo,Sato, Kazuhiko,Sakurai, Hideki
, p. 2243 - 2246 (1987)
Pentacoordinate hydridosiliconates were prepared via the reaction of trichlorosilane with dilithiated hexafluorocumyl alcohol and characterized spectroscopically.The facile reduction of carbonyl compounds with the siliconates is indicative of the highly activated Si-H bond in the anionic hydridosiliconates.
Covalent grafting of cobalt carbonyl cluster on functionalized mesoporous SBA- 15 molecular sieve and its applications towards hydroformylation of 1-octene
Ahmed, Maqsood,Sakthivel, Ayyamperumal
, p. 85 - 90 (2016)
Cobalt carbonyl cluster was anchored through a facile route on the surface of organo-functionalized SBA-15 molecular sieve by post-synthetic approach. The successful grafting of organofunctional ligand and cobalt carbonyl cluster was evident thorough 29Si-MAS NMR, 13C-MAS NMR and FT-IR studies. The resultant cobalt clusters anchored functionalized SBA-15 material (SBA-15-RCo) showed promising catalytic activity on hydroformylation of 1-octene (97% conversion) with excellent selective towards hydroformylated products (90%).
Development of a ruthenium/Phosphite catalyst system for domino hydroformylation-reduction of olefins with carbon dioxide
Liu, Qiang,Wu, Lipeng,Fleischer, Ivana,Selent, Detlef,Franke, Robert,Jackstell, Ralf,Beller, Matthias
, p. 6888 - 6894 (2014)
An efficient domino ruthenium-catalyzed reverse water-gas-shift (RWGS)-hydroformylation-reduction reaction of olefins to alcohols is reported. Key to success is the use of specific bulky phosphite ligands and triruthenium dodecacarbonyl as the catalyst. Compared to the known ruthenium/chloride system, the new catalyst allows for a more efficient hydrohydroxymethylation of terminal and internal olefins with carbon dioxide at lower temperature. Unwanted hydrogenation of the substrate is prevented. Preliminary mechanism investigations uncovered the homogeneous nature of the active catalyst and the influence of the ligand and additive in individual steps of the reaction sequence.
Tandem hydroformylation/hydrogenation over novel immobilized Rh-containing catalysts based on tertiary amine-functionalized hybrid inorganic-organic materials
Gorbunov, Dmitry,Karakhanov, Eduard,Maximov, Anton,Naranov, Evgeny,Nenasheva, Maria,Rosenberg, Edward
, (2021/07/10)
Non-phosphorous rhodium-containing catalysts for direct conversion of olefins to alcohols via tandem hydroformylation/hydrogenation have been designed and synthesized. Interaction between Rh(acac)(CO)2 and tertiary amino groups on the surface of mesoporous hybrid organic-inorganic supports yielded materials which were successfully used in the tandem process. Data obtained for a selected catalyst KN demonstrate that rhodium is in the Rh+1 state highly dispersed on the surface and is bonded with nitrogen atoms both before and after use. Evaluation of the catalytic performance shows high activity (hydroformylation TOF 312 h?1), chemoselectivity and stable hydroformylation yield at least in the first 5 cycles with a decrease in alcohol selectivity. The influence of temperature, reaction time, total pressure, and molar CO/H2 ratio of syngas on oxygenate yields is described. Type of the hydroformylation active sites and possible pathways for the observed decrease in hydrogenation are discussed.
Iridium-Catalyzed Domino Hydroformylation/Hydrogenation of Olefins to Alcohols: Synergy of Two Ligands
Beller, Matthias,Huang, Weiheng,Jackstell, Ralf,Jiao, Haijun,Tian, Xinxin
supporting information, (2022/01/13)
A novel one-pot iridium-catalyzed domino hydroxymethylation of olefins, which relies on using two different ligands at the same time, is reported. DFT computation reveals different activities for the individual hydroformylation and hydrogenation steps in the presence of mono- and bidentate ligands. Whereas bidentate ligands have higher hydrogenation activity, monodentate ligands show higher hydroformylation activity. Accordingly, a catalyst system is introduced that uses dual ligands in the whole domino process. Control experiments show that the overall selectivity is kinetically controlled. Both computation and experiment explain the function of the two optimized ligands during the domino process.
Method for producing a shaped catalyst body
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Page/Page column 29-30, (2021/11/19)
Provided herein is a novel process for producing shaped catalyst bodies in which a mixture having aluminum contents of Al±0 in the range from 80 to 99.8% by weight, based on the mixture used, is used to form a specific intermetallic phase, shaped catalyst bodies obtainable by the process of the invention, a process for producing an active catalyst fixed bed including the shaped catalyst bodies provided herein, the active catalyst fixed beds and also the use of these active catalyst fixed beds for the hydrogenation of organic hydrogenatable compounds or for formate degradation.
Ruthenium-catalysed domino hydroformylation-hydrogenation-esterification of olefins
Beller, Matthias,Dühren, Ricarda,Franke, Robert,Jackstell, Ralf,Kucmierczyk, Peter,Schneider, Carolin
, p. 5777 - 5780 (2021/09/10)
A novel catalytic domino reductive hydroformylation-esterification of olefins is reported. The optimal protocol makes use of an inexpensive Ru carbonyl catalyst and uses acetic acid as both solvent and reactant. In general, moderate to good yields are obtained using aliphatic or aromatic olefins including industrially relevant di-isobutene. This atom-efficient catalytic transformation provides straightforward access to various acetate esters from unfunctionalized olefins.
Directing Selectivity to Aldehydes, Alcohols, or Esters with Diphobane Ligands in Pd-Catalyzed Alkene Carbonylations
Aitipamula, Srinivasulu,Britovsek, George J. P.,Nobbs, James D.,Tay, Dillon W. P.,Van Meurs, Martin
, p. 1914 - 1925 (2021/06/28)
Phenylene-bridged diphobane ligands with different substituents (CF3, H, OMe, (OMe)2, tBu) have been synthesized and applied as ligands in palladium-catalyzed carbonylation reactions of various alkenes. The performance of these ligands in terms of selectivity in hydroformylation versus alkoxycarbonylation has been studied using 1-hexene, 1-octene, and methyl pentenoates as substrates, and the results have been compared with the ethylene-bridged diphobane ligand (BCOPE). Hydroformylation of 1-octene in the protic solvent 2-ethyl hexanol results in a competition between hydroformylation and alkoxycarbonylation, whereby the phenylene-bridged ligands, in particular, the trifluoromethylphenylene-bridged diphobane L1 with an electron-withdrawing substituent, lead to ester products via alkoxycarbonylation, whereas BCOPE gives predominantly alcohol products (n-nonanol and isomers) via reductive hydroformylation. The preference of BCOPE for reductive hydroformylation is also seen in the hydroformylation of 1-hexene in diglyme as the solvent, producing heptanol as the major product, whereas phenylene-bridged ligands show much lower activities in this case. The phenylene-bridged ligands show excellent performance in the methoxycarbonylation of 1-octene to methyl nonanoate, significantly better than BCOPE, the opposite trend seen in hydroformylation activity with these ligands. Studies on the hydroformylation of functionalized alkenes such as 4-methyl pentenoate with phenylene-bridged ligands versus BCOPE showed that also in this case, BCOPE directs product selectivity toward alcohols, while phenylene-bridge diphobane L2 favors aldehyde formation. In addition to ligand effects, product selectivities are also determined by the nature and the amount of the acid cocatalyst used, which can affect substrate and aldehyde hydrogenation as well as double bond isomerization.
Selective Production of Linear Aldehydes and Alcohols from Alkenes using Formic Acid as Syngas Surrogate
Chen, Junjun,Hua, Kaimin,Liu, Xiaofang,Deng, Yuchao,Wei, Baiyin,Wang, Hui,Sun, Yuhan
, p. 9919 - 9924 (2021/05/31)
Performing carbonylation without the use of carbon monoxide for high-value-added products is an attractive yet challenging topic in sustainable chemistry. Herein, effective methods for producing linear aldehydes or alcohols selectively with formic acid as both carbon monoxide and hydrogen source have been described. Linear-selective hydroformylation of alkenes proceeds smoothly with up to 88 % yield and >30 regioselectivity in the presence of single Rh catalyst. Strikingly, introducing Ru into the system, the dual Rh/Ru catalysts accomplish efficient and regioselective hydroxymethylation in one pot. The present processes utilizing formic acid as syngas surrogate operate simply under mild condition, which opens a sustainable way for production of linear aldehydes and alcohols without the need for gas cylinders and autoclaves. As formic acid can be readily produced via CO2 hydrogenation, the protocols represent indirect approaches for chemical valorization of CO2.
