10486-19-8Relevant articles and documents
Hydroformylation of higher olefins in aqueous biphasic medium using rhodium-sulfoxantphos catalyst: Activity and selectivity study
Pagar, Nitin S.,Deshpande, Raj M.
, p. 2061 - 2066 (2020)
Hydroformylation of higher olefins such as 1-hexene, 1-octene, 1-decene and 1-dodecene has been studied in an aqueous biphasic medium using water-soluble Rh-sulfoxantphos complex catalyst. The effect of temperature, presence of various co-solvents and concentration of co-solvent on the reaction rate and chemo and regioselectivity was investigated. N-Methyl pyrrolidone (NMP) was found to be the best co-solvent, which enhances the rate dramatically (4-96 fold) as compared to the reactions in aqueous-organic biphasic medium for hydroformylation of higher olefins. Catalyst recycle study was performed to check the leaching of metal in organic phase.
Crucial role of additives in iridium-catalyzed hydroformylation
Behr, Arno,K?mper, Alexander,Nickel, Martin,Franke, Robert
, p. 243 - 248 (2015)
Abstract This paper presents the new highly selective iridium-catalyzed hydroformylation of 1-octene with an Ir(cod)(acac)/PPh3/salt catalyst system. The addition of inorganic salts such as LiCl suppresses the hydrogenation of 1-octene and increases the yield of desired hydroformylation products. Even low amounts of LiCl (LiCl/Ir = 2/1) significantly increase the chemoselectivity of aldehydes up to 94% with a 1-octene conversion of 90% within 7 h. This catalyst is applicable to other alkenes such as 1-pentene or 1-dodecene. The high selectivities and the remarkable activity of the optimized iridium catalyst are promising in terms of successfully implementing on an industrial scale in the future.
Analysis of the reaction network for the Rh-catalyzed hydroformylation of 1-dodecene in a thermomorphic multicomponent solvent system
Markert,Brunsch,Munkelt,Kiedorf,Behr,Hamel,Seidel-Morgenstern
, p. 287 - 295 (2013)
The hydroformylation of 1-dodecene was studied using Rh(acac)(CO) 2 and a ligand as a catalyst in a thermomorphic multicomponent solvent (TMS) system consisting of N,N-dimethylformamide, decane and the olefin. High n-aldehyde/iso-aldehydes ratios were obtained with the bidentate phosphite ligand biphephos. In systematic preliminary investigations suitable catalyst/ligand-ratios and catalyst concentrations were determined. In order to derive a simplified reaction network, semi-batch experiments were performed measuring responses to perturbations of pressure and feed composition. From the results obtained the main branches of the reaction network could be identified comprising also isomerizations and hydrogenations of n- and iso-dodecenes. For this simplified reaction network a catalytic cycle is suggested providing the basis for the formulation of a more detailed mechanistic kinetic model.
Enzyme Activity by Design: An Artificial Rhodium Hydroformylase for Linear Aldehydes
Jarvis, Amanda G.,Obrecht, Lorenz,Deuss, Peter J.,Laan, Wouter,Gibson, Emma K.,Wells, Peter P.,Kamer, Paul C. J.
, p. 13596 - 13600 (2017)
Artificial metalloenzymes (ArMs) are hybrid catalysts that offer a unique opportunity to combine the superior performance of natural protein structures with the unnatural reactivity of transition-metal catalytic centers. Therefore, they provide the prospect of highly selective and active catalytic chemical conversions for which natural enzymes are unavailable. Herein, we show how by rationally combining robust site-specific phosphine bioconjugation methods and a lipid-binding protein (SCP-2L), an artificial rhodium hydroformylase was developed that displays remarkable activities and selectivities for the biphasic production of long-chain linear aldehydes under benign aqueous conditions. Overall, this study demonstrates that judiciously chosen protein-binding scaffolds can be adapted to obtain metalloenzymes that provide the reactivity of the introduced metal center combined with specifically intended product selectivity.
Rhodium nanoparticles as catalysts in the hydroformylation of 1-dodecene and their recycling in thermomorphic solvent systems
Behr, Arno,Brunsch, Yvonne,Lux, Adrian
, p. 2680 - 2683 (2012)
Rhodium nanoparticles of about 3 nm in size were provided in stabilizing polar solvents. These nanoparticles were used in hydroformylation reactions of higher alkenes; 1-dodecene was used as a model substance. With a metal/substrate ratio of 1:1000, a 97% yield of aldehydes was achieved and an n/iso ratio of 72:28 was obtained. The addition of the ligand biphephos decelerated the reaction, but high n/iso ratios of up to 96:4 were achieved. For the first time, an effective catalyst recycling of these long-term stable nanoparticles in a thermomorphic multicomponent solvent (TMS) system was performed. The catalyst phase was recycled for three runs without any evident loss in activity. TEM images proved that after the recycling runs rhodium nanoparticles were still the active catalyst.
Enhancing the stability of the Rh/ZnO catalyst by the growth of ZIF-8 for the hydroformylation of higher olefins
Chen, Lele,Gao, Zhaohua,Ren, Wanzhong,Song, Huaxing,Tian, Jinghao,Wang, Wenhua,Wei, Haisheng
, p. 34381 - 34386 (2020)
Hydroformylation of olefins is one of the most important industrial processes for aldehyde production. Therein, the leaching of active metals for heterogeneous catalysts is an important issue in the hydroformylation reaction, particularly for higher olefins to produce higher alcohols. Here, different Rh/ZnO catalysts with diverse ZnO as a support were investigated and a home-made ZnO50support was selected to prepare the Rh/ZnO50?ZIF-8 core-shell structure catalyst, which was synthesized by the growth of ZIF-8 with ZnO50as the sacrificed template to afford Zn source. Compared with the Rh/ZnO50catalyst, the Rh/ZnO50?ZIF-8 catalyst demonstrated a better cyclic stability in the hydroformylation of 1-dodecene. Combining the experiment and characterization results, it was concluded that the ZIF-8 shell on the Rh/ZnO50catalyst effectively prevented the leaching of metal Rh into the reaction solution. Moreover, the Rh/ZnO50?ZIF-8 catalyst exhibited good universality for other higher olefins. This work provides a useful guideline for immobilizing the active species in heterogeneous catalysts for the hydroformylation reaction.
Temperature-controlled catalyst recycling in homogeneous transition-metal catalysis: Minimization of catalyst leaching
Brunsch, Yvonne,Behr, Arno
, p. 1586 - 1589 (2013)
Reduce-reuse-recycle! One of the challenges in applied homogeneous catalysis is the efficient recycling of the valuable metal catalyst. The catalyst recycling concept of temperature-controlled multicomponent solvent systems was successfully applied to the hydroformylation of long-chain alkenes. The factors that signficantly influence catalyst leaching and how it can be minimized effectively were systematically investigated for the first time. Copyright
Catalytic Asymmetric Synthesis of Isoxazolines from Silyl Nitronates
Han, Xiaoyu,Dong, Li,Geng, Caiwei,Jiao, Peng
, p. 3194 - 3197 (2015)
1,3-Dipolar cycloadditions of triisopropylsilyl nitronates and 2-alkylacroleins produced isoxazolines bearing a chiral quaternary center in high yields and enantioselectivities with the aid of a chiral oxazaborolidine catalyst. One chiral isoxazoline product was converted to (R)-(+)-Tanikolide in 9 steps in a total yield of 43%. (Chemical Equation Presented).
From alkenes to alcohols by cobalt-catalyzed hydroformylation-reduction
Achonduh, George,Yang, Qian,Alper, Howard
, p. 1241 - 1246 (2015)
The cobalt-catalyzed hydroformylation of alkenes in the presence of a range of novel cyclic phosphine ligands was investigated. The effect of various parameters such as solvents, additives, cobalt/phosphine ratio, CO/H2 (1:2), and nature of the alkenes was examined. The results revealed that both terminal and internal alkenes are hydroformylated in high yields to give mainly linear products at moderate temperature and syn gas pressure. The linearity ranges from 43 to 85%, with Lim-10 giving the highest proportion of linear product.
Efficient water-soluble catalytic system RhI-CAP for biphasic hydroformylation of olefins
Eliseev, Oleg L.,Bondarenko, Tatyana N.,Britvin, Sergey N.,Khodorchenko, Polina P.,Lapidus, Albert L.
, p. 264 - 266 (2018)
Rhodium-catalysed hydroformylation of styrene and aliphatic olefins under biphasic conditions in the presence of watersoluble 1,4,7-triaza-9-phosphatricyclo[5.3.2.14,9]tridecane (CAP) chemoselectively affords aldehydes. Multiple catalyst reuse without loss in performance is demonstrated.
Multiphasic aqueous hydroformylation of 1-alkenes with micelle-like polymer particles as phase transfer agents
Bibouche, Bachir,Peral, Daniel,Stehl, Dmitrij,S?derholm, Viktor,Schom?cker, Reinhard,Von Klitzing, Regine,Vogt, Dieter
, p. 23332 - 23338 (2018)
Micelle-like polymer particles have been applied in aqueous multiphasic hydroformylation reactions of long chain alkenes. These colloids act as phase transfer agents for the nonpolar substrates and as carriers for the catalyst bearing sulfonated ligands by electrostatic attraction. The catalyst performance and the phase separation were optimized with special focus on the conversion, selectivity and catalyst recovery, as those are key points in multiphasic systems to achieve a feasible industrial process. The effect on the catalyst performance of the number of sulfonate groups and electron withdrawing trifluoromethyl groups in the ligand has been studied. The approach was successfully demonstrated for 1-alkenes from 1-hexene to 1-dodecene. For 1-octene, a TOF of more than 3000 h?1 could be achieved at a substrate to catalyst ratio of 80?000, while keeping the rhodium and phosphorous leaching below 1 ppm. In repetitive batch experiments the catalyst was recycled four times, yielding an accumulated TON of more than 100?000 for 1-octene.
Rhodium-catalysed hydroformylation of branched 1-alkenes; bulky phosphite vs. triphenylphosphine as modifying ligand
Van Rooy, Annemiek,De Bruijn, Jacques N. H.,Roobeek, Kees F.,Kamer, Paul C. J.,Van Leeuwen, Piet W. N. M.
, p. 69 - 73 (1996)
The influence of alkyl substituents in 1-alkene substrates in the rhodium-catalysed hydroformylation in the presence of tris(2-tertbutyl-4-methylphenyl) phosphite has been studied and compared with that observed for the reaction involving the conventional PPh3-modified catalyst. Hindered alkenes underwent hydroformylation at good rates (i.e. 1300 mol (mol Rh)-1 h-1 for 3,3-dimethyl-1-butene as T = 70°C and P = 20 bar (H2-CO)); under mild conditions the rates were only slightly affected by the alkyl substituents. The selectivity towards the linear aldehyde increases progressively with substitution, from 66% for 1-octene up to 100% for 3,3-dimethyl-1-butene, and the proportion of isomerized alkenes remained substantial (up to 17.4% for allylcyclohexane). The differences between the two systems are explained in terms of the different kinetics observed for them.
Water-soluble phosphane-substituted cyclodextrin as an effective bifunctional additive in hydroformylation of higher olefins
Leblond,Potier,Menuel,Bricout,Machut-Binkowski,Landy,Tilloy,Monflier,Hapiot
, p. 3823 - 3830 (2017)
In cyclodextrin (CD)-mediated aqueous biphasic catalysis, favoring contacts between the CD ("host"), the organic substrate ("guest") and the water-soluble catalyst is crucial for the reaction to proceed efficiently at the aqueous/organic interface. Grafting the catalyst onto the CD backbone thus appears as an attractive approach to favor the molecular recognition of the substrate and its subsequent catalytic conversion into products. In this context, a new water-soluble β-CD-based phosphane was synthesized and characterized by NMR, tensiometric and ITC measurements. The β-CD-based phosphane consisted of a 3,3′-disulfonatodiphenyl phosphane connected to the primary face of β-CD by a dimethyleneamino spacer. Intra- and intermolecular inclusion processes of one of the two sulfophenyl groups into the β-CD cavity were identified in water. However, the association constant (Ka) related to the β-CD/sulfophenyl group couple was low. Accordingly, the inclusion process was easily displaced upon coordination to rhodium complexes. The efficacy of the resulting Rh-complex coordinated by β-CD-based phosphanes was assessed in Rh-catalyzed hydroformylation of higher olefins. The catalytic system proved to be far more successful and efficient than a system consisting of supramolecularly interacting phosphanes and CDs. The catalytic activity was up to 30-fold higher while the chemo- and regioselectivities remain rather unchanged.
Selective Isomerization of 1,2-Epoxyalkanes to Aldehydes with Lithium Dialkylamides
Yanagisawa, Akira,Yasue, Katsutaka,Yamamoto, Hisashi
, p. 2103 - 2104 (1994)
Reaction of a variety of 1,2-epoxyalkanes with 2.5 equiv. of bulky metal amide - lithium 2,2,6,6-tetramethylpiperidide - affords the corresponding aldehydes exclusively in high yields; this is the first example of base-promoted isomerization of monosubstituted epoxides to aldehydes.
An efficient conversion of carboxylic acids to one-carbon degraded aldehydes via 2-hydroperoxy acids
Akakabe, Yoshihiko,Nyuugaku, Takeshi
, p. 1370 - 1371 (2007)
After the formation of dianions of a carboxylic acid with lithium diisopropylamide, oxygen was bubbled into the solution to produce 2-hydroperoxy acid. Then the reaction mixture was acidified with a 2N HCl solution and subsequently elevated to 50°C to afford the aldehyde with the loss of one carbon atom. Even saturated (C10-C20) and unsaturated (C18:1) carboxylic acids were converted into the odd aldehydes (C9-C19, C17:1) in high yields. This conversion was found to be an efficient method for the preparation of carboxylic acids (Cn) to one-carbon degraded aldehydes (Cn-1) via 2-hydroperoxy acids.
Nonaqueous Biphasic Hydroformylation of Long Chain Alkenes Catalyzed by Water Soluble Phosphine Rhodium Catalyst with Polyethylene Glycol Instead of Water
Zhao, Yuanjiang,Liu, Yanli,Wei, Jianzhang,Fu, Haiyan,Zheng, Xueli,Yuan, Maolin,Li, Ruixiang,Chen, Hua
, p. 438 - 442 (2018)
Abstract: The application of polyethylene glycol (donated as PEG), as an environmentally benign solvent instead of water, in rhodium catalyzed hydroformylation of long chain alkenes by using water soluble phosphine BISBIS or TPPTS (TPPTS: sodium salt of sulfonated triphenylphosphine, BISBIS: sodium salt of sulfonated 2,2′-bis(diphenylphosphinomethyl)-1,1′-biphenyl) is herein reported. The conversion of long chain alkenes in PEG-200 could reach above 95.0% after a short reaction time (15?min). In addition, an efficient phase separation and recycling of PEG-200 and catalyst were achieved. The leaching of rhodium into product phase detected by ICP-AES was less than 0.06?wt% of the initial amount. Graphical Abstract: [Figure not available: see fulltext.].
Sequential reactions from catalytic hydroformylation toward the synthesis of amino compounds
Almeida, Ana R.,Carrilho, Rui M.B.,Peixoto, Andreia F.,Abreu, Artur R.,Silva, Artur,Pereira, Mariette M.
, p. 2389 - 2395 (2017)
Different families of new amino compounds were efficiently synthesized, through optimized sequential processes, involving rhodium catalyzed hydroformylation as the key step. The selection of appropriate hydroformylation catalytic systems and reaction conditions allowed obtaining aldehydes derived from several n-alkyl olefins, cholest-4-ene and 3-vinyl-1H-indole, which were subsequently transformed, in one-pot, in to α-amino acids via hydroformylation/Strecker reaction, and in to tertiary amines via hydroaminomethylation, with excellent yields.
Polymer-supported sulfinimidoyl chloride as a useful reagent for oxidation of various alcohols to the corresponding carbonyl compounds
Matsuo, Jun-ichi,Kawana, Asahi,Pudhom, Khanitha,Mukaiyama, Teruaki
, p. 250 - 251 (2002)
Polymer-supported sulfinimidoyl chloride was prepared in four steps from chloromethyl polystyrene resin. Stoichiometric and catalytic oxidations of various alcohols to the corresponding carbonyl compounds were carried out cleanly by using the prepared polymer-bound oxidant.
Heterogeneous hydroformylation of long-chain alkenes in IL-in-oil Pickering emulsion
Tao, Lin,Zhong, Mingmei,Chen, Jian,Jayakumar, Sanjeevi,Liu, Lina,Li, He,Yang, Qihua
, p. 188 - 196 (2018)
An efficient heterogeneous catalytic system for hydroformylation of long-chain alkenes is highly desirable for both academy and industry. In this study, an IL-in-oil Pickering emulsion system was employed for heterogeneous hydroformylation of 1-dodecene with Rh-sulfoxantphos as the catalyst and surface modified dendritic mesoporous silica nanospheres (DMSN) as the stabilizer. The IL-in-oil Pickering emulsion system outperformed IL-oil biphase, water-in-oil Pickering emulsion and IL-oil micelle system under similar reaction conditions to afford n/b ratio of 98:2, chemoselectivity of 94% and TOF of 413 h-1, among the highest ever reported for IL-oil biphase hydroformylation of long-chain alkenes. The high efficiency of IL-in-oil Pickering emulsion was primarily attributed to the increased interface area and unique properties of ILs. Studies also revealed that solid stabilizers with large and open pore channels could greatly increase the reaction rate of Pickering emulsion systems by accelerating the diffusion rate. The recyclable IL-in-oil Pickering emulsion is promising not only for hydroformylation of long-chain alkenes but also for catalytic reactions with immiscible liquids.
Catalytic isomerization-hydroformylation of olefins by rhodium salicylaldimine pre-catalysts
Sekoto, Pamela N.,Magengenene, Tseliso M.,Matsinha, Leah C.,Tia, Richard,Darkwa, James,Makhubela, Banothile C. E.
, p. 8751 - 8762 (2020)
A series of new Schiff-base rhodium(i) water-soluble complexes (C1-C3), were prepared and characterized. These complexes served as catalyst precursors for the hydroformylation of 1-octene and resulted in excellent substrate conversions (>98%) with 100% chemoselectivities to aldehydes, under mild conditions. Notably, good regioselectivities towards branched aldehydes were observed clearly demonstrating the catalysts’ ability in thermodynamically favoured isomerization followed by hydroformylation (n/iso ratio ranging between 0.7-1.2). Interestingly, catalystC1uniquely promoted contra-thermodynamic isomerization of 2-octene to 1-octene with up to 50% conversion. The efficacy of catalystC1was further evaluated in the hydroformylation of longer chain olefins (C10-C12), methyl acrylate, ethyl acrylate and styrene. The catalyst displayed conversions >99% with the long chain substrates and much lower conversions with the acrylates. These water-soluble (pre)catalysts were recycled up to three times with no significant loss in catalytic activity and selectivity. Mercury poisoning tests were conducted and the experiments revealed that the conversion of the substrates into aldehydes was due to molecular active catalysts and not as a result of colloidal particles that could have formedin situthrough the decomposition of the catalyst precursor. Finally, the molecular catalyst responsible for activity was established using preliminary computational calculations.
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.
Rhodium-Catalyzed Remote C(sp3)?H Borylation of Silyl Enol Ethers
Li, Jie,Qu, Shuanglin,Zhao, Wanxiang
supporting information, p. 2360 - 2364 (2020/01/02)
A rhodium-catalyzed remote C(sp3)?H borylation of silyl enol ethers (SEEs, E/Z mixtures) by alkene isomerization and hydroboration is reported. The reaction exhibits mild reaction conditions and excellent functional-group tolerance. This method is compatible with an array of SEEs, including linear and branched SEEs derived from aldehydes and ketones, and provides direct access to a broad range of structurally diverse 1,n-borylethers in excellent regioselectivities and good yields. These compounds are precursors to various valuable chemicals, such as 1,n-diols and aminoalcohols.
