- Hydroformylation of higher olefins in aqueous biphasic medium using rhodium-sulfoxantphos catalyst: Activity and selectivity study
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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.
- Pagar, Nitin S.,Deshpande, Raj M.
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- Pickering emulsions based on supramolecular hydrogels: Application to higher olefins' hydroformylation
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Supramolecular hydrogels elaborated from a mixture of native α-cyclodextrin and poly(ethylene glycol)s in water proved to be effective media for higher olefins Rh-catalyzed hydroformylation due to the formation of Pickering emulsions.
- Potier, Jonathan,Menuel, Stephane,Chambrier, Marie-Heleine,Burylo, Laurence,Blach, Jean-Francois,Woisel, Patrice,Monflier, Eric,Hapiot, Frederic
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- Crucial role of additives in iridium-catalyzed hydroformylation
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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.
- Behr, Arno,K?mper, Alexander,Nickel, Martin,Franke, Robert
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- Thermal, Catalytic Conversion of Alkanes to Linear Aldehydes and Linear Amines
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Alkanes, the main constituents of petroleum, are attractive feedstocks for producing value-added chemicals. Linear aldehydes and amines are two of the most important building blocks in the chemical industry. To date, there have been no effective methods for directly converting n-alkanes to linear aldehydes and linear amines. Here, we report a molecular dual-catalyst system for production of linear aldehydes via regioselective carbonylation of n-alkanes. The system is comprised of a pincer iridium catalyst for transfer-dehydrogenation of the alkane using t-butylethylene or ethylene as a hydrogen acceptor working sequentially with a rhodium catalyst for olefin isomerization-hydroformylation with syngas. The system exhibits high regioselectivity for linear aldehydes and gives high catalytic turnover numbers when using ethylene as the acceptor. In addition, the direct conversion of light alkanes, n-pentane and n-hexane, to siloxy-terminated alkyl aldehydes through a sequence of Ir/Fe-catalyzed alkane silylation and Ir/Rh-catalyzed alkane carbonylation, is described. Finally, the Ir/Rh dual-catalyst strategy has been successfully applied to regioselective alkane aminomethylation to form linear alkyl amines.
- Tang, Xinxin,Jia, Xiangqing,Huang, Zheng
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- Analysis of the reaction network for the Rh-catalyzed hydroformylation of 1-dodecene in a thermomorphic multicomponent solvent system
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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.
- Markert,Brunsch,Munkelt,Kiedorf,Behr,Hamel,Seidel-Morgenstern
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- Highly efficient heterogeneous hydroformylation over rh-metalated porous organic polymers: Synergistic effect of high ligand concentration and flexible framework
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A series of diphosphine ligand constructed porous polymers with stable and flexible frameworks have been successfully synthesized under the solvothermal conditions from polymerizing the corresponding vinyl-functionalized diphosphine monomers. These insoluble porous polymers can be swollen by a wide range of organic solvents, showing similar behavior to those of soluble analogues. Rather than just as immobilizing homogeneous catalysts, these porous polymers supported with Rh species demonstrate even better catalytic performance in the hydroformylations than the analogue homogeneous catalysts. The sample extraordinary performance could be attributed to the combination of high ligand concentration and flexible framework of the porous polymers. Meanwhile, they can be easily separated and recycled from the reaction systems without losing any activity and selectivity. This excellent catalytic performance and easy recycling heterogeneous catalyst property make them be very attractive. These diphosphine ligand constructed porous polymers may provide new platforms for the hydroformylation of olefins in the future.
- Sun, Qi,Dai, Zhifeng,Liu, Xiaolong,Sheng, Na,Deng, Feng,Meng, Xiangju,Xiao, Feng-Shou
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- Enzyme Activity by Design: An Artificial Rhodium Hydroformylase for Linear Aldehydes
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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.
- Jarvis, Amanda G.,Obrecht, Lorenz,Deuss, Peter J.,Laan, Wouter,Gibson, Emma K.,Wells, Peter P.,Kamer, Paul C. J.
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- Radical carbonylations using a continuous microflow system
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Radical-based carbonylation reactions of alkyl halides were conducted in a microflow reactor under pressurized carbon monoxide gas. Good to excellent yields of carbonylated products were obtained via radical formylation, carbonylative cyclization and threecomponent coupling reactions, using tributyltin hydride or TTMSS as a radical mediator.
- Fukuyama, Takahide,Rahman, Md. Taifur,Kamata, Naoya,Ryu, Ilhyong
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- Rhodium nanoparticles as catalysts in the hydroformylation of 1-dodecene and their recycling in thermomorphic solvent systems
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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.
- Behr, Arno,Brunsch, Yvonne,Lux, Adrian
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- Synthesis of the novel ligand tris-(3,4-dimethoxylphenyl) phosphine and its catalytic performance in 1-dodecene hydroformylation
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Tris-(3,4-dimethoxylphenyl)phosphine (TDMOPP) was synthesized and used as a ligand for the homogenous hydroformylation of 1-dodecene. The effects of the P/Rh molar ratio and reaction temperature on the activity and regioselectivity were investigated. The results showed that the activity of TDMOPP was about two times higher than that of the traditional triphenylphosphine at a low P/Rh and temperature.
- Yuan, Maolin,Fu, Haiyan,Li, Ruixiang,Chen, Hua,Li, Xianjun
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- Enhancing the stability of the Rh/ZnO catalyst by the growth of ZIF-8 for the hydroformylation of higher olefins
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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.
- Chen, Lele,Gao, Zhaohua,Ren, Wanzhong,Song, Huaxing,Tian, Jinghao,Wang, Wenhua,Wei, Haisheng
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- Temperature-controlled catalyst recycling in homogeneous transition-metal catalysis: Minimization of catalyst leaching
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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
- Brunsch, Yvonne,Behr, Arno
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- Super long-term highly active and selective hydroformylation in a room temperature-solidifiable guanidinium ionic liquid with a polyether tag
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Here we report a novel room temperature-solidifiable guanidinium methanesulfonate with a polyether tag and its use in Rh-catalysed biphasic hydroformylation of higher olefins. This novel ionic liquid can efficiently immobilize the Rh-TPPTS catalyst and render super long-term high activity and chemoselectivity, and no significant loss of activity, selectivity or Rh was observed after thirty-five cycles.
- Jin, Xin,Yang, Daoxing,Xu, Xinfu,Yang, Zhiqiang
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- Catalytic Asymmetric Synthesis of Isoxazolines from Silyl Nitronates
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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).
- Han, Xiaoyu,Dong, Li,Geng, Caiwei,Jiao, Peng
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- Synergetic effect of randomly methylated β-cyclodextrin and a supramolecular hydrogel in Rh-catalyzed hydroformylation of higher olefins
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A significant improvement in Rh-catalyzed hydroformylation of very hydrophobic alkenes was achieved using a biphasic catalytic system consisting of a substrate-containing organic phase and a catalyst-containing hydrogel phase [consisting of poly(ethylene glycol) 20000 (PEG20000) and α-cyclodextrin (α-CD)]. The catalytic performance of the Pickering emulsion that resulted from the formation of α-CD/PEG20000 crystallites at the oil droplet surface proved to be greatly dependent upon the presence of additives. We showed that controlled uploads of randomly methylated β-cyclodextrin (RAME-β-CD) within the supramolecular hydrogel could positively affect both the catalytic activity and chemoselectivity of the hydroformylation reaction. Conversely, no Pickering emulsion could be observed using excess RAME-β-CD, resulting in the subsequent degradation of the catalytic performance. Optical microscopy and optical fluorescence microscopy supported the catalytic results and allowed us to explain the role of RAME-β-CD. Indeed, controlled uploads of RAME-β-CD prevented the saturation of the oil droplet surface. RAME-β-CD acted as a fluidifier of the Pickering emulsion and accelerated the dynamics of exchange between the substrate-containing organic phase and the catalyst-containing hydrogel phase. Morever, RAME-β-CD acted as a receptor that participated in the conversion of the alkene by supramolecular means.
- Potier, Jonathan,Menuel, Stephane,Monflier, Eric,Hapiot, Frederic
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- From alkenes to alcohols by cobalt-catalyzed hydroformylation-reduction
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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.
- Achonduh, George,Yang, Qian,Alper, Howard
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- Continuous Flow Hydroformylation of Alkenes in Supercritical Fluid-Ionic Liquid Biphasic Systems
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A process for the hydroformylation of relatively low volatility alkenes (demonstrated for 1-dodecene) in a continuous flow system is described. The catalyst is dissolved in an ionic liquid while the substrate and gaseous reagents are transported into the reactor dissolved in supercritical CO 2, which simultaneously acts as a transport vector for aldehyde products. Decompression of the fluid mixture downstream yields products which are free of both reaction solvent and catalyst. The use of rhodium complexes of triaryl phosphites leads to ligand degradation through reaction of the ionic liquid with water and subsequent attack of the released HF on the phosphite. Sodium salts of sulfonated phosphines are insufficiently soluble in the ionic liquids to obtain acceptable rates, but replacing the sodium by a cation similar to that derived from the ionic liquid, allows good solubility and activity to be obtained. The nature of the ionic liquid is very important in achieving high rates, with 1-alkyl-3-methylimidazolium bis(trifluoromethanesulfonyl)amides giving the best activity if the alkyl chain is at least C8. Catalyst turnover frequencies as high as 500 h -1 have been observed, with the better rates at higher substrate flow rates. Rhodium leaching into the product stream can be as low as 0.012 ppm, except at low partial pressures of CO/H2, when it is significantly higher. Oxygen impurities in the CO2 feed can lead to oxidation of the phosphine giving higher rates, lower selectivities to the linear aldehyde, increased alkene isomerization and greater leaching of rhodium. However, it is found that under certain process conditions, the supercritical fluid-ionic liquid (SCF-IL) system can be operated continuously for several weeks without any visible sign of catalyst degradation. Comparisons with commercial hydroformylation processes are provided.
- Webb, Paul B.,Sellin, Murielle F.,Kunene, Thulani E.,Williamson, Sylvia,Slawin, Alexandra M. Z.,Cole-Hamilton, David J.
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- Efficient water-soluble catalytic system RhI-CAP for biphasic hydroformylation of olefins
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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.
- Eliseev, Oleg L.,Bondarenko, Tatyana N.,Britvin, Sergey N.,Khodorchenko, Polina P.,Lapidus, Albert L.
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- A novel thermoregulated ionic liquid and organic biphasic system with rh nanoparticles for olefin hydroformylation
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A thermoregulated ionic liquid and organic biphasic system composed of quaternary ammonium-based ionic liquid N,N-dimethyl-N-(2-(2-methoxyethoxy)ethyl) - N-(2-(2-octyloxyethoxy)ethyl) ammonium methanesulfonate (1) and cyclohexane was first applied for the Rh nanoparticle catalyzed hydroformylation of olefins, which allows for not only a highly efficient homogeneous catalytic reaction, but also an easy separation and reuse of catalyst. Under the optimized conditions, various olefins could be converted completely with C98 % selectivity for aldehydes. After reaction, the Rh nanoparticle catalyst could be recovered by simple phase separation and reused for five times without evident loss of activity. Springer Science+Business Media, LLC 2012.
- Xu, Yicheng,Wang, Yanhua,Zeng, Yan,Jiang, Jingyang,Jin, Zilin
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- Multiphasic aqueous hydroformylation of 1-alkenes with micelle-like polymer particles as phase transfer agents
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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.
- Bibouche, Bachir,Peral, Daniel,Stehl, Dmitrij,S?derholm, Viktor,Schom?cker, Reinhard,Von Klitzing, Regine,Vogt, Dieter
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- Selective hydroformylation of olefins over the rhodium supported large porous metal-organic framework MIL-101
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Highly porous and crystalline metal-organic framework MIL-101 has been synthesized and used for the preparation of rhodium supported catalyst. Acetylacetonato(1,5-cyclooctadiene)rhodium(I) has been used as catalyst precursor. The material has been characterized by XRD, XPS, SAXS, FTIR, SEM, TEM, AAS, and nitrogen adsorption. The catalytic properties of Rh@MIL-101 have been investigated in the hydroformylation of olefins with different structure and chain length to the corresponding aldehydes. High conversion and selectivity to n-aldehydes have been achieved in the hydroformylation of n-alk-1-enes. The obtained results show that the rhodium species are highly dispersed and preferentially located at internal and less accessible sites at the supertetrahedral units.
- Van Vu, Toan,Kosslick, Hendrik,Schulz, Axel,Harloff, Joerg,Paetzold, Eckhard,Schneider, Mathias,Radnik, Joerg,Steinfeldt, Norbert,Fulda, Gerhard,Kragl, Udo
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- Rhodium-catalysed hydroformylation of branched 1-alkenes; bulky phosphite vs. triphenylphosphine as modifying ligand
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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.
- Van Rooy, Annemiek,De Bruijn, Jacques N. H.,Roobeek, Kees F.,Kamer, Paul C. J.,Van Leeuwen, Piet W. N. M.
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- Integration of phosphine ligands and ionic liquids both in structure and properties-a new strategy for separation, recovery, and recycling of homogeneous catalyst
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The major limitation of classic biphasic ionic liquid (IL) catalysis is the heavy use of solvent ILs, which not only violates green chemistry principles but also even worsens catalytic efficiency. So it has always been a challenge finding ways to use ILs more efficiently, economically, and greenly to construct highly effective and long term stable IL catalytic systems. In this work, we synthesized a class of room temperature phosphine-functionalized polyether guanidinium ionic liquids (RTP-PolyGILs) by a convenient ion exchange reaction of polyether guanidinium ionic liquids (PolyGILs) with phosphine-sulfonate ligands based on the concept of the integration of both the phosphine ligand and IL. The resulting RTP-PolyGILs existed as liquids at room temperature and possessed dual functions of both the phosphine ligand and solvent IL; therefore they could both form catalysts by complexing with transition metals and act as catalyst carriers, thus achieving the integration of phosphine ligands with ILs both in structure and properties. Based on the unique properties of these multi-functional integrated RTP-PolyGILs, we constructed a highly effective homogeneous catalysis-biphasic separation (HCBS) system for Rh-catalyzed hydroformylation of higher olefins using only a catalytic amount of RTP-PolyGILs (equivalent to 0.025-0.4 mol% of 1-alkenes). Our HCBS system could be flexibly regulated with regard to catalytic performance (activity and linear selectivity) by changing the structure or type of the sulfonated ligand anion on RTP-PolyGILs. Specifically, it presented a TOF value of 3000-26000 h-1 and a linear selectivity of 68%-98% (corresponding to the l/b ratio of 2.2-37.5) with a total turnover number (TTON) of 11000-45000 and an extremely low Rh leaching of only 0.02-0.4 ppm. Therefore, the HCBS system can effectively combine the advantages of both homogeneous (high activity and good selectivity) and biphasic catalysis (easy catalyst separation). We additionally extended the application of the HCBS system to the hydrogenation of olefins to demonstrate the universality of the RTP-PolyGILs in catalytic reactions.
- Jin, Xin,Feng, Jianying,Song, Hongbing,Yao, Jiajun,Ma, Qingqing,Zhang, Mei,Yu, Cong,Li, Shumei,Yu, Shitao
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- Water-soluble phosphane-substituted cyclodextrin as an effective bifunctional additive in hydroformylation of higher olefins
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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.
- Leblond,Potier,Menuel,Bricout,Machut-Binkowski,Landy,Tilloy,Monflier,Hapiot
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- TEMPO-mediated environmentally benign oxidation of primary alcohols to carboxylic acids with poly[4-(diacetoxyiodo)styrene]
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An operationally simple and environmentally benign oxidation of primary alcohols to the corresponding carboxylic acids with a TEMPO-mediated poly[4-(diacetoxyiodo)styrene] system in acetone and water was carried out.
- Tashino, Yousuke,Togo, Hideo
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- Selective Isomerization of 1,2-Epoxyalkanes to Aldehydes with Lithium Dialkylamides
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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.
- Yanagisawa, Akira,Yasue, Katsutaka,Yamamoto, Hisashi
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- Homogeneous hydroformylation of long chain alkenes catalyzed by water soluble phosphine rhodium complex in CH3OH and efficient catalyst cycling
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The hydroformylation of long chain alkenes catalyzed by a water soluble Rh/TPPTS complex (TPPTS: sodium salt of sulfonated triphenylphosphine) in methanol was investigated. The mixture of rhodium precursor HRh(CO)(TPPTS)3, ligand TPPTS, methanol and a long chain alkene becomes a single phase under reaction conditions, which make the hydroformylation reaction proceed homogeneously. Both the conversion of long chain alkene and the selectivity to aldehydes (including the aldehydes forming methylacetals) could reach up to 97.8% and 97.6%, respectively, with 3323 h?1 of TOF (TOF: turnover frequency is defined as the moles of converted alkene per mole of Rh per hour). After the solvent methanol was removed under the reaction temperature, two phases were formed automatically. The colourless product phase could be efficiently separated from the precipitate rhodium catalyst phase by centrifuge. The catalyst was reused for five times without obvious loss of rhodium and the catalytic activity. The rhodium leaching in product mixture was less than 0.03% of the total rhodium.
- Liu, Yan-li,Zhao, Jian-gui,Zhao, Yuan-jiang,Liu, Hui-Min,Fu, Hai-yan,Zheng, Xue-li,Yuan, Mao-lin,Li, Rui-xiang,Chen, Hua
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- An efficient conversion of carboxylic acids to one-carbon degraded aldehydes via 2-hydroperoxy acids
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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.
- Akakabe, Yoshihiko,Nyuugaku, Takeshi
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- Ultrastable 3V-PPh3 polymers supported single Rh sites for fixed-bed hydroformylation of olefins
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The heterogenization of homogeneous catalysts is of critical importance for both fundamental research and practical applications. The key obstacle to industrial applications of heterogenized homogeneous catalysts is the long-term stability of the immobilized molecular complexes. We unambiguously demonstrate in this report that the vinyl-functionalized PPh3 polymers supported single Rh sites (Rh/POL-PPh3) catalyst provided not only excellent catalytic activity but also ultrahigh stability for fixed-bed olefins hydroformylation, which is one of the most important industrial homogeneous catalytic processes for the synthesis of aldehydes and alcohols. HAADF-STEM and EXAFS results indicated that the Rh atoms were present in single Rh sites which were strongly coordinated with the exposed phosphorous atoms of the POL-PPh3 support. The Rh/POL-PPh3 catalyst provided high activity and selectivity because it maintained the catalytic functionalities similar to the homogeneous HRh(CO)(PPh3)3 complex, as demonstrated both by 31P MAS NMR and in situ FT-IR experiments. Thus a reaction mechanism, similar to that over the homogeneous HRh(CO)(PPh3)3 complex, was proposed for olefin hydroformylation over the novel Rh/POL-PPh3 catalyst.
- Jiang, Miao,Yan, Li,Ding, Yunjie,Sun, Qi,Liu, Jia,Zhu, Hejun,Lin, Ronghe,Xiao, Fengshou,Jiang, Zheng,Liu, Jingyue
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- Nonaqueous Biphasic Hydroformylation of Long Chain Alkenes Catalyzed by Water Soluble Phosphine Rhodium Catalyst with Polyethylene Glycol Instead of Water
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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.].
- Zhao, Yuanjiang,Liu, Yanli,Wei, Jianzhang,Fu, Haiyan,Zheng, Xueli,Yuan, Maolin,Li, Ruixiang,Chen, Hua
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- Catalyst-free oxidation of alcohols at room temperature using water as solvent
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An effective, cheap, environmentally benign and catalyst-free oxidation of alcohols was carried out at room temperature using tetra-n-butylammonium Oxone (TBA-OX) as oxidant with moderate to high selectivity for most of the alcohols using water as the solvent.
- Lei, Ziqiang,Yang, Yaoxia,Bai, Xiangzhen
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- Sequential reactions from catalytic hydroformylation toward the synthesis of amino compounds
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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.
- Almeida, Ana R.,Carrilho, Rui M.B.,Peixoto, Andreia F.,Abreu, Artur R.,Silva, Artur,Pereira, Mariette M.
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- Polymer-supported sulfinimidoyl chloride as a useful reagent for oxidation of various alcohols to the corresponding carbonyl compounds
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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.
- Matsuo, Jun-ichi,Kawana, Asahi,Pudhom, Khanitha,Mukaiyama, Teruaki
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- Supramolecular encapsulated rhodium catalysts for branched selective hydroformylation of alkenes at high temperature
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This study reveals that, in contrast to expectations, supramolecular encapsulated rhodium catalysts can be used at industrially relevant temperatures (75-80 °C), providing highly active catalysts. The unprecedented regioselectivity for the branched aldehydes can be retained if high carbon monoxide (CO) concentrations are used.
- Besset, Tatiana,Norman, David W.,Reek, Joost N. H.
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- Heterogeneous hydroformylation of long-chain alkenes in IL-in-oil Pickering emulsion
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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.
- Tao, Lin,Zhong, Mingmei,Chen, Jian,Jayakumar, Sanjeevi,Liu, Lina,Li, He,Yang, Qihua
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- Regioselective functionalization of alkanes by sequential dehydrogenation-hydrozirconation
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We have succeeded in formal regioselective functionalization of alkanes by iridium-catalyzed dehydrogenation, hydrozirconation of the resulting alkenes, and electrophilic reaction of the generated alkylzirconium intermediate.
- Kuninobu, Yoichiro,Ureshino, Tomonari,Yamamoto, Shun-Ichi,Takai, Kazuhiko
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- Catalytic isomerization-hydroformylation of olefins by rhodium salicylaldimine pre-catalysts
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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.
- Sekoto, Pamela N.,Magengenene, Tseliso M.,Matsinha, Leah C.,Tia, Richard,Darkwa, James,Makhubela, Banothile C. E.
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- Enantiospecific total synthesis of the squalene synthase inhibitors (-)-CJ-13,982 and its enantiomer from a common intermediate
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The total syntheses of both the natural and unnatural enantiomers of the alkyl citrate natural product CJ-13,982 (1) from the common d-ribose-derived acid 6 are described.
- Sturgess, Dayna,Chen, Zongjia,White, Jonathan M.,Rizzacasa, Mark A.
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- Methyl-modified cage-type phosphorus ligand and preparation method thereof Preparation method and application thereof
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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.
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Paragraph 0075-0084; 0087-0088
(2021/09/15)
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- Selective Production of Linear Aldehydes and Alcohols from Alkenes using Formic Acid as Syngas Surrogate
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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.
- Chen, Junjun,Hua, Kaimin,Liu, Xiaofang,Deng, Yuchao,Wei, Baiyin,Wang, Hui,Sun, Yuhan
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p. 9919 - 9924
(2021/05/31)
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- Rhodium-Catalyzed Remote C(sp3)?H Borylation of Silyl Enol Ethers
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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.
- Li, Jie,Qu, Shuanglin,Zhao, Wanxiang
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supporting information
p. 2360 - 2364
(2020/01/02)
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- Iron Catalyzed Hydroformylation of Alkenes under Mild Conditions: Evidence of an Fe(II) Catalyzed Process
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Earth abundant, first row transition metals offer a cheap and sustainable alternative to the rare and precious metals. However, utilization of first row metals in catalysis requires harsh reaction conditions, suffers from limited activity, and fails to tolerate functional groups. Reported here is a highly efficient iron catalyzed hydroformylation of alkenes under mild conditions. This protocol operates at 10-30 bar syngas pressure below 100 °C, utilizes readily available ligands, and applies to an array of olefins. Thus, the iron precursor [HFe(CO)4]-[Ph3PNPPh3]+ (1) in the presence of triphenyl phosphine catalyzes the hydroformylation of 1-hexene (S2), 1-octene (S1), 1-decene (S3), 1-dodecene (S4), 1-octadecene (S5), trimethoxy(vinyl)silane (S6), trimethyl(vinyl)silane (S7), cardanol (S8), 2,3-dihydrofuran (S9), allyl malonic acid (S10), styrene (S11), 4-methylstyrene (S12), 4-iBu-styrene (S13), 4-tBu-styrene (S14), 4-methoxy styrene (S15), 4-acetoxy styrene (S16), 4-bromo styrene (S17), 4-chloro styrene (S18), 4-vinylbenzonitrile (S19), 4-vinylbenzoic acid (S20), and allyl benzene (S21) to corresponding aldehydes in good to excellent yields. Both electron donating and electron withdrawing substituents could be tolerated and excellent conversions were obtained for S11-S20. Remarkably, the addition of 1 mol % acetic acid promotes the reaction to completion within 16-24 h. Detailed mechanistic investigations revealed in situ formation of an iron-dihydride complex [H2Fe(CO)2(PPh3)2] (A) as an active catalytic species. This finding was further supported by cyclic voltammetry investigations and intermediacy of an Fe(0)-Fe(II) species was established. Combined experimental and computational investigations support the existence of an iron-dihydride as the catalyst resting state, which then follows a Fe(II) based catalytic cycle to produce aldehyde.
- Pandey, Swechchha,Raj, K. Vipin,Shinde, Dinesh R.,Vanka, Kumar,Kashyap, Varchaswal,Kurungot, Sreekumar,Vinod,Chikkali, Samir H.
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supporting information
p. 4430 - 4439
(2018/04/05)
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- Based on [...] functionalized polyether alkyl guanidine salt ion liquid of the two-phase hydroformylation of olefins method
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The present invention relates to a method for biphasic hydroformaylation of olefins based on a phosphine-functionalized polyether alkyl guanidine salt ionic liquid. A biphasic catalytic system is used in the method, wherein the catalytic system consists of the phosphine-functionalized polyether alkyl guanidine salt ionic liquid, a rhodium catalyst, a reaction substrate - olefins and a reaction product - aldehydes; liquid/liquid biphasic hydroformylation of olefins is performed at a certain reaction temperature and syngas pressure; the phosphine-functionalized polyether alkyl guanidine salt ionic liquid acts both as a phosphine ligand and as a rhodium catalyst carrier; there is no need to add any other ionic liquid to the system; separation and recycling of the rhodium catalyst are realized by liquid/liquid biphasic separation after the reaction; the rhodium catalyst is capable of being recycled for multiple times with no obvious decrease in catalytic activity or selectivity; the TOF value of the system reaches 240-2700h-1; and the highest catalytic cycle cumulative TON value reaches 47138.
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Paragraph 0045; 0046; 0047; 0062
(2018/09/26)
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- Supported rhodium liquid metal catalysts for the hydroformylation of olefins
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The hydroformylation of olefins in supported room temperature liquid metals was developed, and the supported Rh liquid metal catalysts (Rh SLMCs) showed unprecedented activity and high selectivity for the hydroformylation of olefins to aldehydes. The turnover frequency is up to 7000?h?1, much higher than that of homogeneous RhCl3?+?3PPh3 catalyst. Moreover, the Rh SLMCs can be recovered conveniently without obvious deactivation, and the total turnover number is up to 250?000. The active Rh(I) catalyst formed in situ can be reduced back to Rh(0) by the free electrons in liquid metal when H2/CO gas is emitted, and thus Rh is not leaked into the organic solvent. Long-chain olefins, cycloolefins and styrenes were applied, and the corresponding aldehydes were obtained in good to excellent yields.
- Sun, Hao,Guo, Wanwan,Liu, Junmei,Feng, Zhipeng,Li, Ruyue,Zhou, Xuyang,Huang, Jun
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- A kind of [...] functionalized polyether pyridine salt ion liquid and its olefin hydroformylation reaction in the application of the
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The present invention relates to a phosphine-functionalized polyether pyridinium salt ionic liquid and a method for biphasic hydroformaylation of olefins based on the phosphine-functionalized polyether pyridinium salt ionic liquid. A biphasic catalytic system is used in the method, wherein the catalytic system consists of a phosphine-functionalized polyether pyridinium salt ionic liquid, a rhodium catalyst, a reaction substrate, olefins, and a reaction product, aldehydes; liquid/liquid biphasic hydroformylation of olefins is performed at a certain reaction temperature and syngas pressure; the phosphine-functionalized polyether pyridinium salt ionic liquid acts both as a phosphine ligand and as a rhodium catalyst carrier; there is no need to add any other ionic liquid to the system; and separation and recycling of the rhodium catalyst are realized by liquid/liquid biphasic separation after the reaction. The catalytic system provided by the present invention is high in catalytic activity. The rhodium catalyst is capable of being recycled for many times with no obvious decrease in catalytic activity or selectivity.
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Paragraph 0026; 0027; 0033; 0056; 0058
(2018/05/24)
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- A kind of [...] functionalized polyether quaternary phosphonium ionic liquid and its olefin hydroformylation reaction in the application of the (by machine translation)
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The invention relates to a functionalized polyether quaternary phosphonium salt [...] ionic liquid, and a functionalized polyether quaternary phosphonium salt based on [...] ionic liquid two-phase hydroformylation of olefins of the method, the method uses a two-phase catalytic system, the catalytic system is composed of [...] functionalized polyether quaternary phosphonium ion liquid, rhodium catalyst and reaction substrate olefin and reaction aldehyde composition, in a certain reaction temperature and the synthesis gas is conducted under a pressure liquid/liquid two-phase hydroformylation reaction, [...] functionalized polyether quaternary phosphonium ionic liquid is phosphine, at the same time also acts as the rhodium catalyst carrier, system do not need in in addition introducing other ionic liquid, after the reaction through a simple liquid/liquid two-phase separation [...] separation and recycle of the catalyst, the catalytic system has higher catalytic activity, rhodium catalyst can be circulated many times, catalytic activity and selectivity without significant decrease. (by machine translation)
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Paragraph 0052-0054; 0067-0069
(2017/11/16)
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- Tetronics/cyclodextrin-based hydrogels as catalyst-containing media for the hydroformylation of higher olefins
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The rhodium-catalyzed hydroformylation of alkenes has been investigated under biphasic conditions using combinations of α-cyclodextrin (α-CD) and poloxamines (Tetronics). Thermo-responsive hydrogels containing the Rh-catalyst are formed under well-defined conditions of concentration. Hydrogels consisting of the reverse-sequential Tetronic 90R4 prove to be more effective than those containing the conventional sequential Tetronic 701. The presence of α-CD is crucial to provoke the decantation of the multiphasic system once the reaction is complete. Optimized conditions (CO/H2 pressure, Rh-precursors, phosphanes, etc.) show that the catalytic system is especially applicable to the hydroformylation of terminal alkenes. The catalytic performance remains unchanged upon recycling as the hydrogel matrix prevents the oxidation of the phosphane.
- Chevry,Vanbésien,Menuel,Monflier,Hapiot
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p. 114 - 123
(2017/08/14)
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- A kind of [...] functionalized polyether piperidine salt ion liquid and its olefin hydroformylation reaction in the application of the
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The present invention relates to a phosphine-functionalized polyether piperidine salt ionic liquid and a method for biphasic hydroformaylation of olefins based on the phosphine-functionalized polyether piperidine salt ionic liquid. The method uses a biphasic catalytic system, wherein the catalytic system consists of a phosphine-functionalized polyether piperidine salt ionic liquid, a rhodium catalyst, the reaction substrate, olefins and the reaction product, aldehydes; liquid/liquid biphasic hydroformylation of olefins is performed at a certain reaction temperature and syngas pressure; the phosphine-functionalized polyether piperidine salt ionic liquid acts both as a phosphine ligand and as a rhodium catalyst carrier; there is no need to add any other ionic liquid to the system; and separation and recycling of the rhodium catalyst are realized by liquid/liquid biphasic separation after the reaction. The catalytic system provided by the present invention is high in catalytic activity. The rhodium catalyst is capable of being recycled for many times with no obvious decrease in catalytic activity and selectivity.
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Paragraph 0025-0027; 0061-0063; 0076-0078
(2017/11/16)
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- Method for high-selectivity preparation of normal aldehyde through olefin two-phase hydroformylation on basis of polyether alkyl guanidinium ionic liquid
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The invention relates to a method for high-selectivity preparation of normal aldehyde through olefin two-phase hydroformylation on the basis of a polyether alkyl guanidinium ionic liquid. According to the method, a two-phase catalytic system is adopted, the catalytic system comprises a polyether alkyl guanidinium ionic liquid PGILs with room temperature liquid-solid phase change characteristics, a rhodium catalyst, diphosphine ligands, a reaction substrate olefin and a reaction product aldehyde, a liquid/liquid two-phase hydroformylation reaction is performed at certain reaction temperature and under certain synthesis gas pressure, and the rhodium catalyst is recovered and cycled through simple two-phase separation after the reaction ends. The catalytic system has high catalytic activity with, high selectivity, ultralong service life and very low rhodium catalyst loss amount, wherein the TOF value reaching 130-240 h; the area selectivity of normal aldehyde reaches 96%-98%; the catalytic cycle accumulated TON value is 40,000 or above at most; the rhodium catalyst loss amount is only 0.02%-0.1%.
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Paragraph 0074-0075
(2017/01/09)
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- Method for high-selectivity preparation of normal aldehyde through olefin two-phase hydroformylation on basis of polyether pyridinium ionic liquid
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The invention relates to a method for high-selectivity preparation of normal aldehyde through olefin two-phase hydroformylation on the basis of a polyether pyridinium ionic liquid. According to the method, a two-phase catalytic system is adopted, the catalytic system comprises a polyether pyridinium ionic liquid PPYILs with room temperature liquid-solid phase change characteristics, a rhodium catalyst, diphosphine ligands, a reaction substrate olefin and a reaction product aldehyde, a liquid/liquid two-phase hydroformylation reaction is performed at certain reaction temperature and under certain synthesis gas pressure, and the rhodium catalyst is recovered and cycled through simple two-phase separation after the reaction ends. The catalytic system has high catalytic activity, high selectivity, ultralong service life and very low rhodium catalyst loss amount, wherein the TOF value reaches 160-220 h; the area selectivity of normal aldehyde reaches 96%-98%; the catalytic cycle accumulated TON value is approximately 40,000; the rhodium catalyst loss amount is only 0.06%-0.2%.
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Paragraph 0025-0027; 0070-0072; 0076-0078
(2017/03/08)
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- Method of preparing normal aldehyde in highly selective manner through olefin two-phase hydroformylation on basis of polyether morpholine salt ion liquid
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The invention relates to a method of preparing normal aldehyde in a highly selective manner through olefin two-phase hydroformylation on the basis of polyether morpholine salt ion liquid. The method includes: adopting a two-phase catalysis system which is composed of polyether morpholine salt ion liquid with room temperature liquid-solid phase transition characteristics, rhodium catalyst, diphosphine ligand, reaction substrate olefin and reaction product aldehyde; performing liquid/liquid two-phase hydroformylation at certain reaction temperature and synthetic gas pressure; after reaction is finished, recycling and circulating the rhodium catalyst through simple two-phase separation, wherein the rhodium catalyst can be circulated for use for dozens of times without obviously lowering catalytic activity and selectivity. TOF value of the system reaches 260-2000 h-1, catalytic circulating accumulated TON value reaches higher than 35000 to maximum extent, regioselectivity of the normal aldehyde is up to 96-98%, an rhodium loss is only 0.01-0.10%.
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Paragraph 0025-0027; 0079-0081
(2017/06/24)
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- Synthesis of 6-Hydroxysphingosine and α-Hydroxy Ceramide Using a Cross-Metathesis Strategy
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(Chemical Equation Presented) In this paper, a new synthetic route toward 6-hydroxysphingosine and α-hydroxy ceramide is described. The synthesis employs a cross-metathesis to unite a sphingosine head allylic alcohol with a long-chain fatty acid alkene that also bears an allylic alcohol group. To allow for a productive CM coupling, the sphingosine head allylic alcohol was protected with a cyclic carbonate moiety and a reactive CM catalyst system, consisting of Grubbs II catalyst and CuI, was employed.
- Wisse, Patrick,De Geus, Mark A. R.,Cross, Gen,Van Den Nieuwendijk, Adrianus M. C. H.,Van Rooden, Eva J.,Van Den Berg, Richard J. B. H. N.,Aerts, Johannes M. F. G.,Van Der Marel, Gijsbert A.,Codée, Jeroen D. C.,Overkleeft, Herman S.
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p. 7258 - 7265
(2015/07/27)
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- Enantioselective Hydroformylation of 1-Alkenes with Commercial Ph-BPE Ligand
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A rhodium complex, in conjunction with commercially available Ph-BPE ligand, catalyzes the branch-selective asymmetric hydroformylation of 1-alkenes and rapidly generates α-chiral aldehydes. A wide range of terminal olefins including 1-dodecene were examined, and all delivered high enantioselectivity (up to 98:2 er) as well as good branch:linear ratios (up to 15:1). (Chemical Equation Presented).
- Yu, Zhiyong,Eno, Meredith S.,Annis, Alexandra H.,Morken, James P.
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supporting information
p. 3264 - 3267
(2015/07/15)
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- Photodegradation of Hydrophobic Pyridineketoximes in Toluene and Heptane
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The goal of the research was to study the reactivity of the hydrophobic 2- and 3-pyridineketoximes under exposure to UV-VIS light. The photodegradation was conducted in both toluene and heptane for 10 h under atmosphere of argon. Ten-hour irradiation experiments demonstrated that the pyridineketoximes underwent the facile E-Z photoisomerization, photo-Beckmann rearrangement, and to a lesser extent, the photosubstitution to the pyridine ring. From LC-MS and NMR analysis of the irradiated solutions, it was found that the photosubstitution proceeded to give the corresponding 6-substituted 2- or 3-pyridylketoxime via the replacement of the ring hydrogen by the benzyl or heptyl group. The photo-Beckmann rearrangement led to the formation of the corresponding amides, but also other products formed in the photo-decomposition reaction.
- Wieszczycka, Karolina,Zembrzuska, Joanna
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p. 786 - 796
(2015/07/07)
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- METHOD FOR HYDROFORMYLATION OF UNSATURATED COMPOUNDS
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The invention relates to a method for hydroformylation of unsaturated compounds such as olefins and alkynes using mixtures of synthesis gas (CO/H2), in which either the unsaturated compounds and a catalyst are heated to a reaction temperature of 60 to 200° C. and the synthesis gas is then added, or the unsaturated compounds and the catalyst are brought into contact with pure CO at normal temperature in a preformation step, then are heated to reaction temperature and on reaching the reaction temperature the CO is replaced by the synthesis gas. The pressure is 1 to 200 bar and the CO:H2 ratio in the synthesis gas is in the range from 1:1 to 50:1. The iridium catalyst used comprises a phosphorus-containing ligand in the iridium:ligand ratio in the range from 1:1 to 1:100. With high catalyst activities and low catalyst use, very high turnover frequencies are achieved.
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Paragraph 0091
(2014/02/16)
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- Selective hydroformylation-acetalization of various olefins using simple and efficient Rh-phosphinite complex catalyst
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A simple and efficient Rh-phosphinite complex catalyst was studied for the selective hydroformylation of various olefins. The influence of various reaction parameters including the effect of temperature, pressure, catalyst loading, time, and solvents was studied. The protocol was also applied for the synthesis of various acetals via tandem hydroformylation-acetalization of olefins in alcohols as solvents. High activity and selectivity for acetal formation was achieved in the absence of co-catalysts with admirable substrate to catalyst mole ratio (TON 2500). The developed protocol works for a wide range of olefins to synthesize corresponding aldehydes and acetals under optimized reaction conditions.
- Khan, Shoeb R.,Bhanage, Bhalchandra M.
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p. 5998 - 6001
(2013/10/22)
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- Selective reduction of carboxylic acids to aldehydes through manganese catalysed hydrosilylation
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The direct reduction of carboxylic acids to disilylacetals was achieved through a manganese catalyzed hydrosilylation reaction in the presence of triethylsilane under mild conditions, at r.t. and under UV irradiation (350 nm). The aldehydes were obtained in good to excellent yields after acidic hydrolysis.
- Zheng, Jianxia,Chevance, Soizic,Darcel, Christophe,Sortais, Jean-Baptiste
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p. 10010 - 10012
(2013/10/22)
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- Thermoregulated phase-transfer rhodium nanoparticle catalyst for hydroaminomethylation of olefins
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Rh nanoparticles used as catalysts for hydroaminomethylation reaction is reported for the first time. An efficient and recyclable Rh nanoparticle catalyst stabilized by thermoregulated ligand Ph2P(CH 2CH2O)nCH3 (n = 16) was studied for the hydroaminomethylation of olefins in the aqueous/1-butanol biphasic system through thermoregulated phase-transfer catalysis, which allows not only for a homogeneous catalytic reaction, but also for an easy biphasic separation. Under the optimized conditions, the conversion of 1-octene and the product amine selectivity were as high as 99% and 97%, respectively. After reaction, the Rh nanoparticle catalyst can be separated from products by simple phase separation and recycled directly for the next run.
- Li, Kaoxue,Wang, Yanhua,Xu, Yicheng,Li, Wenjiang,Niu, Mingming,Jiang, Jingyang,Jin, Zilin
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- From olefins to alcohols: Efficient and regioselective ruthenium-catalyzed domino hydroformylation/reduction sequence
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Exploring the alternatives: Ruthenium imidazoyl phosphine complexes catalyze the domino hydroformylation/reduction of alkenes to alcohols in good yields and with good selectivities (see scheme). Linear aliphatic alcohols are synthesized under reaction conditions typically used in industrial hydroformylations. Copyright
- Fleischer, Ivana,Dyballa, Katrin Marie,Jennerjahn, Reiko,Jackstell, Ralf,Franke, Robert,Spannenberg, Anke,Beller, Matthias
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supporting information
p. 2949 - 2953
(2013/04/10)
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- Rhodium complexes stabilized by phosphine-functionalized phosphonium ionic liquids used as higher alkene hydroformylation catalysts: Influence of the phosphonium headgroup on catalytic activity
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Monodentate phosphine-functionalized phosphonium ionic liquids (PFILs) were employed as ligands for Rh complexes and used in the hydroformylation of higher alkenes. Three PFILs were designed by varying the length of the P-alkyl chain attached to the phosphonium moiety, for alkyl = methyl (1), butyl (2), octyl (3), in order to tune their solubility properties. In all PFILs, the phosphonium unit is linked to a diphenylphosphino functionality by an undecyl linker, with bis(trifluoromethylsulfonyl)imide as counter anion. These PFILs were combined with a Rh(i) precursor, [Rh(acac)(CO)2], to provide a biphasic hydroformylation catalyst for the transformation of 1-octene, 1-decene and 1-dodecene using tetradecyltributylphosphonium bis(trifluoromethylsulfonyl) imide, [P4,4,4,14]NTf2 as a solvent. Good activities and excellent selectivities were obtained for these PFILs-Rh(i) complexes. Variation of the P-alkyl length in the PFIL ligand influenced the stability, catalytic activity and selectivity of the PFIL-stabilized catalyst.
- Luska, Kylie L.,Demmans, Karl Z.,Stratton, Samantha A.,Moores, Audrey
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p. 13533 - 13540
(2013/01/15)
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