112-44-7Relevant articles and documents
One-pot conversion of primary alcohols to α-oxygenated alkanals with tempo in combination with molecular oxygen and ruthenium complex
Inokuchi, Tsutomu,Nakagawa, Keiichi,Torii, Sigeru
, p. 3223 - 3226 (1995)
Reaction of primary alcohols with an oxidizing system composed of 4-BzOTEMPO (2 equiv.), RuCl2(PPh3)3 as a catalyst, and molecular oxygen leads to concomitant oxidation and substitution, giving the corresponding α-oxygenated alkanals. Similar reaction of secondary alcohols terminates at the stage of oxidation of hydroxyl group, forming the ketones, selectively.
Polyether phosphite for hydroformylation of higher olefins in non-aqueous system and catalyst recovery
Liu, Xiaozhong,Li, Hongmei,Wang, Yanhua,Jin, Zilin
, p. 83 - 90 (2002)
A new rhodium catalyst recyling system for non-aqueous hydroformylation of 1-decene is described using a polyether phosphite, OPGPP with a polyether chain of over 19 ethylene glycol units. The corresponding rhodium complexes formed in situ are active for non-aqueous hydroformylation of 1-decene. The catalysts precipitated from the reaction mixture on cooling to room temperature or lower and were reused up to six times without obvious decrease in activity. P loss in the seventh reaction run was detected to be 0.92%. Complex OPGPP/Ru3(CO)3 formed in situ has also been proved to be a moderate catalyst for the non-aqueous hydroformylation of 1-decene. The catalysts retained considerable activity up to 87.1% after four successive reaction runs.
TEMPO radical polymer grafted silicas as solid state catalysts for the oxidation of alcohols
Saito, Kei,Hirose, Koji,Okayasu, Teruyuki,Nishide, Hiroyuki,Hearn, Milton T. W.
, p. 9752 - 9756 (2013)
TEMPO polymer-grafted silicas were synthesized by "grafting from" and "grafting to" methods using RAFT polymerization, and their catalytic activities as a new class of solid state catalyst for oxidation reactions with alcohols demonstrated.
Rhodium catalyzed hydroformylation of 1-decene in low melting mixtures based on various cyclodextrins and N,N′-dimethylurea
Ferreira, Michel,Jér?me, Fran?ois,Bricout, Hervé,Menuel, Stéphane,Landy, David,Fourmentin, Sophie,Tilloy, Sébastien,Monflier, Eric
, p. 62 - 65 (2015)
Different low melting mixtures (LMMs) based on N,N′-dimethylurea (DMU) and various cyclodextrin (CD) derivatives were synthetized. The melting point was weakly affected by the size and the chemical modification of CD. By contrast, the chemical modification of CD led to a decrease in viscosity of the LMMs. These mixtures were evaluated as solvent in rhodium-catalyzed hydroformylation reaction of 1-decene. The LMM based on DMU/RAME-β-CD (70/30) allowed reaching the highest catalytic activity (1980 h- 1). The influence of several factors was studied and it was established that the conversion increased with the 1-decene solubility and decreased with the LMM viscosity.
Low melting mixtures based on β-cyclodextrin derivatives and N,N′-dimethylurea as solvents for sustainable catalytic processes
Jerome, Francois,Ferreira, Michel,Bricout, Herve,Menuel, Stephane,Monflier, Eric,Tilloy, Sebastien
, p. 3876 - 3880 (2014)
β-Cyclodextrin series and N,N′-dimethylurea formed low melting mixtures able to immobilize organometallic species based on sulfonated phosphanes. Hydroformylation and Tsuji-Trost reactions were efficiently performed in these new solvents which led to new recyclable catalytic systems. This journal is the Partner Organisations 2014.
Cetyltrimethylammonium bromochromate: A new and efficient oxidant for organic substrates
Ghammamy, Shahriar,Eimanieh, Hossein,Mohammady, Mohammad Kazem
, p. 601 - 607 (2007)
Cetyltrimethylammonium bromochromate is a versatile reagent for the effective and selective oxidation of organic substrates, particularly for alcohols, under mild conditions. Copyright Taylor & Francis Group, LLC.
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Lieberman
, p. 1114 (1955)
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Rhodium complexes non-covalently bound to cyclodextrins: Novel water-soluble supramolecular catalysts for the biphasic hydroformylation of higher olefins
Sueur, Benoit,Leclercq, Loic,Sauthier, Mathieu,Castanet, Yves,Mortreux, Andre,Bricout, Herve,Tilloy, Sebastien,Monflier, Eric
, p. 6228 - 6236 (2005)
A new class of cationic α-cyclodextrins bearing 2-hydroxy-3-trime- thylammoniopropyl groups has been synthesised. We investigated their efficiency as mass-transfer promoters in a biphasic hydroformylation reaction catalysed by a rhodium trisulfonated triphenylphosphine system. These cationic α-cyclodextrins greatly increased the reaction rate, the chemoselectivity, and, surprisingly, the linear-to-branched aldehyde ratio. We attributed this unexpected enhancement of the linear-to-branched aldehyde ratio to the in situ formation of new catalytic supramolecular species obtained by ion-exchange between the catalyst ligand and the cationic α-cyclodextrins.
Water-soluble triphenylphosphane-3,3′,3″-tricarboxylate (m-TPPTC) ligand and methylated cyclodextrins: A new combination for biphasic rhodium-catalyzed hydroformylation of higher olefins
Tilloy, Sebastien,Genin, Emilie,Hapiot, Frederic,Landy, David,Fourmentin, Sophie,Genet, Jean-Pierre,Michelet, Veronique,Monflier, Eric
, p. 1547 - 1552 (2006)
The methylated cyclodextrins/m-TPPTC [tris(m-carboxyphenyl)phosphane trilithium salt] couples proved to be more efficient than the well-known methylated cyclodextrins/TPPTS [tris(m-sulfonatophenyl)phosphane trisodium salt] systems in terms of activities and selectivities to perform the Rh-catalyzed hydroformylation of higher olefins in an aqueous-organic system. The interactions cyclodextrins/m-TPPTC have been fully studied by NMR spectroscopy.
Kinetics of hydroformylation of 1-decene using carbon-supported ossified HRh(CO)(TPPTS)3 catalyst
Pagar, Nitin S.,Deshpande, Raj M.
, p. 112 - 122 (2019)
The kinetics of hydroformylation of 1-decene has been investigated using a carbon-supported ossified HRh(CO)(TPPTS)3/Ba catalyst in a temperature range of 343–363?K. The effect of concentration of 1-decene, catalyst loading, partial pressure of H2 and CO, and stirring speed on the reaction rate has been investigated. A first-order dependence was observed for catalyst concentration and hydrogen partial pressure. The rate showed a typical case of substrate inhibition for high 1-decene concentration. The rate varied with a linear dependence on PCO up to a CO partial pressure of 5–6?MPa in contrast to the general trends; for most of the rhodium-phosphine catalyzed hydroformylation reactions, severe inhibition of rate is observed with an increase in CO pressure. A rate equation has been proposed, which was found to be in good agreement with the observed rate data within the limit of experimental errors. The kinetic parameters and activation energy values have been reported.
Cyclodextrin/amphiphilic phosphane mixed systems and their applications in aqueous organometallic catalysis
Ferreira, Michel,Bricout, Herve,Azaroual, Nathalie,Landy, David,Tilloy, Sebastien,Hapiot, Frederic,Monflier, Eric
, p. 1337 - 1346 (2012)
When mixed with a water-soluble phosphane capable of self-assembling into micelles, native or modified β-cyclodextrins (β-CDs) show very contrasting behavior depending on their neutral or ionic nature. In the post-micellar region, neutral β-CDs led to a micelle destructuring. Conversely, micelles remained stable over a well-defined range of ionic β-CD concentrations. In that case, the micelle destruction was only observed when using a large excess of ionic β-CDs. The catalytic performances of these micellar systems have been evaluated in a rhodium-catalyzed hydroformylation reaction of 1-decene. We showed that, using ionic β-CDs, the catalytic activity could be improved without a detrimental impact upon the regioselectivity. A linear/branched aldehyde ratio as high as 8.6 could be achieved. The best results were obtained with stoichiometric quantities of ionic randomly methylated β-CDs with respect to the phosphane with a beneficial effect on the decantation at the end of the reaction. Copyright
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Matsuda et al.
, p. 3016,3017, 3019 (1978)
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Pillar5arenes as Supramolecular Hosts in Aqueous Biphasic Rhodium-Catalyzed Hydroformylation of Long Alkyl-chain Alkenes
Benatmane, Missipssa,Cousin, Kévin,Laggoune, Nérimel,Menuel, Stéphane,Monflier, Eric,Woisel, Patrice,Hapiot, Frédéric,Potier, Jonathan
, p. 5306 - 5313 (2018)
Aqueous biphasic catalysis continues to attract strong interest, especially when very hydrophobic substrates are concerned. Indeed, their insolubility in water strongly limit their transformation by water-soluble organometallic catalysts. To improve contacts between the substrate-containing organic phase and the catalyst-containing phase, one of the best solutions consists in using interfacial additives capable of supramolecularly recognize the substrate and/or the catalyst. In the present study, modified pillar5arenes are considered as interfacial additives and their performance is assessed in Rh-catalyzed hydroformylation of long alkyl-chain alkenes (higher olefins). Pillar5arenes substituted by carboxylate functions and methyl groups P5 A-(Me)10-x-(CH2COOMe)x are compared to pillar5arenes substituted by polyethylene glycol (PEG) chains (P5 A-(Me)5-(PEG)5 and P5 A-(PEG)10). Utilization of P5 A-(Me)10-x-(CH2COOMe)x leads to high conversion and regioselectivity (linear/branched aldehyde ratio) in Rh-catalyzed hydroformylation of 1-decene and 1-hexadecene. Compared with other interfacial additives such as modified cyclodextrins, the studied pillar5arenes show lower chemo-selectivity, similar catalytic activity and higher regioselectivity.
Polymer-supported nitroxyl radical catalyst for selective aerobic oxidation of primary alcohols to aldehydes
Gilhespy, Michelle,Lok, Martin,Baucherel, Xavier
, p. 1085 - 1086 (2005)
PS-TEMPO, a polymer-supported 2,2,6,6-tetramethyl-piperidine-N-oxyl (TEMPO), was successfully applied as a recyclable, active and selective catalyst for the oxidation of primary aliphatic and benzylic alcohols to aldehydes by molecular oxygen in the presence of Co(NO3)2 and Mn(NO3)2 as co-catalysts. The Royal Society of Chemistry 2005.
Concurrent Catalytic Reduction/Stoichiometric Oxidation Using Oligomerically Ligated Catalysts and Polymer-Bound Reagents
Bergbreiter, David E.,Chandran, Rama
, p. 4792 - 4793 (1985)
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Microbial biosynthesis of medium-chain 1-alkenes by a nonheme iron oxidase
Rui, Zhe,Li, Xin,Zhu, Xuejun,Liu, Joyce,Domigan, Bonnie,Barr, Ian,Cate, Jamie H. D.,Zhang, Wenjun
, p. 18237 - 18242 (2014)
Aliphatic medium-chain 1-alkenes (MCAEs, ～10 carbons) are "drop-in" compatible next-generation fuels and precursors to commodity chemicals. Mass production of MCAEs from renewable resources holds promise for mitigating dependence on fossil hydrocarbons. An MCAE, such as 1-undecene, is naturally produced by Pseudomonas as a semivolatile metabolite through an unknown biosynthetic pathway. We describe here the discovery of a single gene conserved in Pseudomonas responsible for 1-undecene biosynthesis. The encoded enzyme is able to convert medium-chain fatty acids (C10-C14) into their corresponding terminal olefins using an oxygen-activating, nonheme iron-dependent mechanism. Both biochemical and X-ray crystal structural analyses suggest an unusual mechanism of β-hydrogen abstraction during fatty acid substrate activation. Our discovery unveils previously unidentified chemistry in the nonheme Fe(II) enzyme family, provides an opportunity to explore the biology of 1-undecene in Pseudomonas, and paves the way for tailored bioconversion of renewable raw materials to MCAE-based biofuels and chemical commodities.
Rhodium phosphino-enolate complexes as chemo- and regioselective catalysts for the hydroformylation of styrenes
Uh, Yoon-Seo,Boyd, Alaina,Little, Vanessa R.,Jessop, Philip G.,Hesp, Kevin D.,Cipot-Wechsler, Judy,Stradiotto, Mark,McDonald, Robert
, p. 1869 - 1872 (2010)
The catalytic utility of [κ2-{3-iPr 2P-2-O-indene}Rh(COD)] (COD = η4-1,5-cyclooctadiene) 1a in the hydroformylation of styrenes was examined. Complex 1a was shown to be an effective pre-catalyst in benzene and tetrahydrofuran, exhibiting good conversions to aldehyde and high branched o-linear selectivity for styrene, 4-chlorostyrene, and 4-methylstyrene under reasonably mild conditions (1000 psi syngas; 1.8 mol% Rh, 45 °C, 2-5 h). Under analogous conditions, the iridium congener of 1a proved inactive for hydroformylation. The synthesis and crystallographic characterization of the new complex [κ2-{2- iPr2PC6H4O}Rh(COD)] 2 is also reported; the catalytic performance of 2 in the hydroformylation of styrene was found to be comparable to that of 1a under similar catalytic conditions. We report herein on the use of rhodium phosphino-enolate complexes as effective pre-catalysts for the hydroformylation of styrene substrates, exhibiting high branched o-linear selectivity under relatively mild conditions.
Multicatalytic approach to one-pot stereoselective synthesis of secondary benzylic alcohols
Casnati, Alessandra,Lichosyt, Dawid,Lainer, Bruno,Veth, Lukas,Dydio, Pawe?
supporting information, p. 3502 - 3506 (2021/05/10)
One-pot procedures bear the potential to rapidly build up molecular complexity without isolation and purification of consecutive intermediates. Here, we report multicatalytic protocols that convert alkenes, unsaturated aliphatic alcohols, and aryl boronic acids into secondary benzylic alcohols with high stereoselectivities (typically >95:5 er) under sequential catalysis that integrates alkene cross-metathesis, isomerization, and nucleophilic addition. Prochiral allylic alcohols can be converted to any stereoisomer of the product with high stereoselectivity (>98:2 er, >20:1 dr).
Atomically dispersed Rh on hydroxyapatite as an effective catalyst for tandem hydroaminomethylation of olefins
Gun, Gong,Li, Liusha,Li, Xiao,Lin, Tiejun,Qin, Tingting,Zhong, Liangshu
, (2021/07/07)
Tandem hydroaminomethylation is an efficient and green route for one-pot synthesis of amines directly from olefins. Herein, heterogeneous hydroxyapatite (HAP) supported single-atom Rh catalyst was prepared and used for tandem hydroaminomethylation of olefins. Characterization techniques confirmed the atomic dispersion of Rh species on HAP. Up to 99% conversion of 1-hexene with high selectivity to the desired amines (93.2%) was obtained over 0.5Rh1/HAP catalyst. Mechanism study demonstrated that the first hydroformylation step during the tandem catalytic process was rate-determining. Compared with the Rh nanoparticles on other oxide supports (Mg3Al, MgO and Al2O3), the atomically dispersed Rh sites on HAP ensured the high hydroformylation activity, thereby guaranteed the outstanding catalytic performance for the total tandem process. Furthermore, various corresponding amines can be obtained with satisfactory yields over 0.5Rh1/HAP catalyst from a wide scope of olefins or amines substrates.
Unexpected Reactions of α,β-Unsaturated Fatty Acids Provide Insight into the Mechanisms of CYP152 Peroxygenases
Jiang, Yuanyuan,Li, Shengying,Li, Zhong,Peng, Wei,Tang, Dandan,Wang, Binju,You, Cai,Zhao, Yue
supporting information, p. 24694 - 24701 (2021/10/14)
CYP152 peroxygenases catalyze decarboxylation and hydroxylation of fatty acids using H2O2 as cofactor. To understand the molecular basis for the chemo- and regioselectivity of these unique P450 enzymes, we analyze the activities of three CYP152 peroxygenases (OleTJE, P450SPα, P450BSβ) towards cis- and trans-dodecenoic acids as substrate probes. The unexpected 6S-hydroxylation of the trans-isomer and 4R-hydroxylation of the cis-isomer by OleTJE, and molecular docking results suggest that the unprecedented selectivity is due to OleTJE’s preference of C2?C3 cis-configuration. In addition to the common epoxide products, undecanal is the unexpected major product of P450SPα and P450BSβ regardless of the cis/trans-configuration of substrates. The combined H218O2 tracing experiments, MD simulations, and QM/MM calculations unravel an unusual mechanism for Compound I-mediated aldehyde formation in which the active site water derived from H2O2 activation is involved in the generation of a four-membered ring lactone intermediate. These findings provide new insights into the unusual mechanisms of CYP152 peroxygenases.
