16630-91-4Relevant academic research and scientific papers
Chemo- And regioselective hydroformylation of alkenes with CO2/H2over a bifunctional catalyst
Hua, Kaimin,Liu, Xiaofang,Wei, Baiyin,Shao, Zilong,Deng, Yuchao,Zhong, Liangshu,Wang, Hui,Sun, Yuhan
supporting information, p. 8040 - 8046 (2021/11/01)
As is well known, CO2 is an attractive renewable C1 resource and H2 is a cheap and clean reductant. Combining CO2 and H2 to prepare building blocks for high-value-added products is an attractive yet challenging topic in green chemistry. A general and selective rhodium-catalyzed hydroformylation of alkenes using CO2/H2 as a syngas surrogate is described here. With this protocol, the desired aldehydes can be obtained in up to 97% yield with 93/7 regioselectivity under mild reaction conditions (25 bar and 80 °C). The key to success is the use of a bifunctional Rh/PTA catalyst (PTA: 1,3,5-triaza-7-phosphaadamantane), which facilitates both CO2 hydrogenation and hydroformylation. Notably, monodentate PTA exhibited better activity and regioselectivity than common bidentate ligands, which might be ascribed to its built-in basic site and tris-chelated mode. Mechanistic studies indicate that the transformation proceeds through cascade steps, involving free HCOOH production through CO2 hydrogenation, fast release of CO, and rhodium-catalyzed conventional hydroformylation. Moreover, the unconventional hydroformylation pathway, in which HCOOAc acts as a direct C1 source, has also been proved to be feasible with superior regioselectivity to that of the CO pathway.
Methyl-modified cage-type phosphorus ligand and preparation method thereof Preparation method and application thereof
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Paragraph 0075-0084; 0087-0088, (2021/09/15)
The invention discloses a methyl-modified cage-type phosphorus ligand, a preparation method and application thereof, in particular to a synthesis design, wherein methyl is further introduced on a phenyl ring of triphenylphosphine, and a methyl-modified cage-type phosphorus ligand is synthesized, and when a methyl meta-substituted cage-type phosphorus ligand is used as a hydroformylation reaction catalyst the proportion of n-structural aldehyde and isomeric aldehyde is 2.6. TOF-1 The methyl-substituted cage-type phosphorus ligand is excellent in performance, stable in property and recyclable, has excellent substrate applicability in the hydroformylation catalytic reaction, has a good industrial application prospect, and has very important significance in metal organic catalysis.
Encapsulated liquid nano-droplets for efficient and selective biphasic hydroformylation of long-chain alkenes
Zhang, Xiaoli,Wei, Juan,Zhang, Xiaoming
supporting information, p. 14134 - 14138 (2019/09/18)
Aqueous nano-droplets of homogeneous Rh-TPPTS catalyst encapsulated within the cavity of hollow silica nanospheres were fabricated for biphasic hydroformylation of long-chain alkenes, which showed significant reaction rate enhancement effects and improved aldehyde selectivity.
CYCLIC PEPTIDE ANTIBIOTICS
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Paragraph 00277, (2019/04/11)
Provided herein are antibacterial compounds, wherein the compounds in some embodiments have broad spectrum bioactivity. In various embodiments, the compounds act by inhibition of lipoprotein signal peptidase II (LspA), a key protein in bacteria. Pharmaceutical compositions and methods for treatment using the compounds described herein are also provided.
Rhodium-Complex-Catalyzed Hydroformylation of Olefins with CO2and Hydrosilane
Ren, Xinyi,Zheng, Zhiyao,Zhang, Lei,Wang, Zheng,Xia, Chungu,Ding, Kuiling
supporting information, p. 310 - 313 (2016/12/30)
A rhodium-catalyzed one-pot hydroformylation of olefins with CO2, hydrosilane, and H2has been developed that affords the aldehydes in good chemoselectivities at low catalyst loading. Mechanistic studies indicate that the transformation is likely to proceed through a tandem sequence of poly(methylhydrosiloxane) (PMHS) mediated CO2reduction to CO and a conventional rhodium-catalyzed hydroformylation with CO/H2. The hydrosilylane-mediated reduction of CO2in preference to aldehydes was found to be crucial for the selective formation of aldehydes under the reaction conditions.
Rhodium nanoparticles as precursors for the preparation of an efficient and recyclable hydroformylation catalyst
Garcia, Marco A. S.,Oliveira, Kelley C. B.,Costa, Jean C. S.,Corio, Paola,Gusevskaya, Elena V.,Dos Santos, Eduardo N.,Rossi, Liane M.
, p. 1566 - 1572 (2015/05/27)
Despite all the advances in the application of nanoparticle (NP) catalysts, they have received little attention in relation to the hydroformylation reaction. Herein, we present the preparation of a hydroformylation catalyst through the immobilization of air-stable rhodium NPs onto a magnetic support functionalized with chelating phosphine ligands, which serves as an alternative to air-sensitive precursors. The catalyst was active in hydroformylation and could be used in successive reactions with negligible metal leaching. The interaction between the rhodium NPs and the diphenylphosphine ligand was evidenced by an enhancement in the Raman spectrum of the ligand. Changes occurred in the Raman spectrum of the catalyst recovered after the reaction, which suggests that the rhodium NPs are precursors of active molecular species that are formed in situ. The supported catalyst was active for successive reactions even after it was exposed to air during the recycling runs and was easily recovered through magnetic separation. Long live the catalyst! The heterogenization of rhodium catalysts onto a magnetic support and recovery without loss of metal, reactivity, and selectivity is discussed. Rhodium nanoparticles are used as catalyst precursors, and the active species are studied by using Raman spectroscopy.
Rhodium-containing hypercross-linked polystyrene as a heterogeneous catalyst for the hydroformylation of olefins in supercritical carbon dioxide
Lyubimov, Sergey E.,Rastorguev, Eugenie A.,Lubentsova, Kseniya I.,Korlyukov, Alexander A.,Davankov, Vadim A.
, p. 1116 - 1119 (2013/04/10)
A simple procedure for the incorporation of rhodium nanoparticles into a hypercross-linked polystyrene matrix is developed. The prepared heterogeneous catalyst shows high activity in the hydroformylation of olefins in supercritical carbon dioxide, and can be recycled six times without any noticeable decrease in productivity.
Stable fluorophosphines: Predicted and realized ligands for catalysis
Fey, Natalie,Garland, Michael,Hopewell, Jonathan P.,McMullin, Claire L.,Mastroianni, Sergio,Orpen, A. Guy,Pringle, Paul G.
supporting information; experimental part, p. 118 - 122 (2012/03/26)
Ligand maps lead to treasure! The activity of complexes of fluorophosphines (R2PF) in catalytic hydroformylation and hydrocyanation is predicted from a ligand map. However, the instability of R2PF to disproportionation is well-documented. Examples of R2PF ligands (see scheme) are described that are stabilized to such an extent that they can be used in catalysis and are shown to be highly effective.
Pyrazoles as ligands for the Rh-catalyzed hydroformylation of alkenes in supercritical carbon dioxide
Lyubimov,Rastorguev,Davankov
, p. 2356 - 2359 (2013/10/01)
Activity of pyrazole ligands in hydroformylation of a number of unsaturated terminal substrates in supercritical carbon dioxide (scCO2) in the presence of Rh-catalyst was studied. The ligands without free NH group at position 1 of the pyrazole ring were found to be active. The use of scCO 2 as the reaction medium served to reach a higher conversion and regioselectivity of hydroformylation as compared to those in toluene.
Self-assembly of a confined rhodium catalyst for asymmetric hydroformylation of unfunctionalized internal alkenes
Gadzikwa, Tendai,Bellini, Rosalba,Dekker, Henk L.,Reek, Joost N. H.
supporting information; experimental part, p. 2860 - 2863 (2012/03/26)
A chiral supramolecular ligand has been assembled and applied to the rhodium-catalyzed asymmetric hydroformylation of unfunctionalized internal alkenes. Spatial confinement of the metal center within a chiral pocket results in reversed regioselectivity and remarkable enantioselectivities.
