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Methyl-modified cage-type phosphorus ligand and preparation method thereof Preparation method and application thereof
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)

ALDEHYDE GENERATION VIA ALKENE HYDROFORMYLATION
Aldehyde generation includes providing a first input stream, a second input, and an alkene substrate to a reactor system. The first input stream includes a catalyst, a ligand, and an organic solvent. The second input stream includes a mixture of carbon monoxide (CO) and hydrogen gas (H2). The alkene substrate is in either gaseous form or liquid form, the liquid form of the alkene substrate being provided with the first input stream, the gaseous form of the alkene substrate being provided with the second input stream. The reactor system includes a first reactor and a second reactor, where the second reactor is gas permeable and positioned within the first reactor.
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Paragraph 0035; 0079-0081

(2021/09/26)

Chemo- And regioselective hydroformylation of alkenes with CO2/H2over a bifunctional catalyst
As is well known, CO2 is an attractive renewable C1 resource and H2 is a cheap and clean reductant. Combining CO2 and H2 to prepare building blocks for high-value-added products is an attractive yet challenging topic in green chemistry. A general and selective rhodium-catalyzed hydroformylation of alkenes using CO2/H2 as a syngas surrogate is described here. With this protocol, the desired aldehydes can be obtained in up to 97% yield with 93/7 regioselectivity under mild reaction conditions (25 bar and 80 °C). The key to success is the use of a bifunctional Rh/PTA catalyst (PTA: 1,3,5-triaza-7-phosphaadamantane), which facilitates both CO2 hydrogenation and hydroformylation. Notably, monodentate PTA exhibited better activity and regioselectivity than common bidentate ligands, which might be ascribed to its built-in basic site and tris-chelated mode. Mechanistic studies indicate that the transformation proceeds through cascade steps, involving free HCOOH production through CO2 hydrogenation, fast release of CO, and rhodium-catalyzed conventional hydroformylation. Moreover, the unconventional hydroformylation pathway, in which HCOOAc acts as a direct C1 source, has also been proved to be feasible with superior regioselectivity to that of the CO pathway.
Hua, Kaimin,Liu, Xiaofang,Wei, Baiyin,Shao, Zilong,Deng, Yuchao,Zhong, Liangshu,Wang, Hui,Sun, Yuhan
supporting information
p. 8040 - 8046
(2021/11/01)

Insight into decomposition of formic acid to syngas required for Rh-catalyzed hydroformylation of olefins
Formic acid (FA) is one kind of important bulk chemicals, which is recognized as a sustainable and eco-friendly energy carrier to transport H2 via dehydrogenation or CO via decarbonylation. Expectantly, FA upon decomposition into H2 and CO could be used as the syngas alternative for hydroformylation. In this paper, the behaviors of FA to release H2 as well as CO following the distinct pathways were carefully investigated for the first time, and then established a new hydroformylation protocol free of syngas. It was found that the atmospheric hydroformylation of olefins with formic acid (FA) as syngas alternative was smoothly fulfilled over Xantphos (L1) modified Rh-catalyst under mild conditions (80 °C, Rh concentration 1 mol %, 14 h), resulting in >90% conversion of the olefins along with the high selectivity to the target aldehydes (>93%). By using FA as syngas source, the side-reaction of olefin-hydrogenation was greatly depressed. The in situ FT-IR and the high-pressure 1H NMR spectroscopic analyses were applied to reveal how FA behaves dually as CO surrogate and hydrogen source over L1-Rh(acac)(CO)2 catalytic system, based on which the deeply insight into the catalytic mechanism of hydroformylation of olefins with FA as syngas alternative was offered.
Liu, Lei,Chen, Xiao-Chao,Yang, Shu-Qing,Yao, Yin-Qing,Lu, Yong,Liu, Ye
p. 406 - 415
(2020/12/07)

Rh-catalyzed highly regioselective hydroformylation to linear aldehydes by employing porous organic polymer as a ligand
In this work, we developed a new structural porous organic polymer containing biphosphoramidite unit, which can be used as a solid bidentate phosphorous ligand for rhodium-catalyzed solvent-free higher olefins hydroformylation. The resultant catalyst demonstrated unprecedently high regioselectivity to linear aldehydes and could be readily recovered for successive reuses with good stability in both catalytic activity and regioselectivity. This journal is
Wang, Zhaozhan,Yang, Yong
p. 29263 - 29267
(2020/10/06)

Bimetallic Paddlewheel-type Dirhodium(II,II) Acetate and Formamidinate Complexes: Synthesis, Structure, Electrochemistry, and Hydroformylation Activity
Classical hydroformylation catalysts use mononuclear rhodium(I) complexes as precursors; however, very few examples of bimetallic systems have been reported. Herein, we report fully substituted dirhodium(II,II) complexes (C1-C6) containing acetate and diphenylformamidinate bridging ligands (L1-L4). The structure and geometry around these paddlewheel-type, bimetallic cores were confirmed by single-crystal X-ray diffraction. The complexes C3-C6 show electrochemical redox reactions, with the expected reduction (Rh24+/3+) and two oxidation (Rh24+/5+ and Rh25+/6+) electron transfer processes. Furthermore, the bimetallic complexes were evaluated as catalyst precursors for the hydroformylation of 1-octene, with the acetate-containing complexes (C1 and C2) showing near quantitative conversion (>99%) of 1-octene, excellent activity and chemoselectivity toward aldehydes (>98%), with moderate regioselectivity toward linear products. Replacement of the acetate with diphenylformamidinate ligands (complexes C3-C6) yielded moderate-to-good chemoselectivity and regioselectivity, favoring linear aldehydes.
Casimiro, Anna,De Doncker, Stephen,Kotze, Izak A.,Ngubane, Siyabonga,Smith, Gregory S.
p. 12928 - 12940
(2020/09/15)

A new air-stable and reusable tetraphosphine ligand for rhodium-catalyzed hydroformylation of terminal olefins at low temperature
Tetraphosphine and bisphosphine ligands were synthesized, characterized and employed in Rh-catalyzed hydroformylation of 1-octene and 1-hexene. Conversion of over 97.7% and aldehyde yield of 94.1% were achieved at 60°C, 20?bar. This remarkable performance could also be retained at lower temperature (i.e. 40°C) by prolonging the reaction time. The tetraphosphine ligand-modified Rh catalyst could be reused for at least seven successive runs with catalytic activity and selectivity almost unchanged; the catalyst was separated from the products and recycled directly in homogeneous hydroformylation, indicating that the catalyst might have good stability. 31P NMR and high-resolution mass spectral characterization hinted that the reason for the reusability of the catalyst might be that the tetraphosphine ligand is relatively air-stable and is probably slowly oxidized during the recycling runs. The tetraphosphine ligand has four phosphorus atoms to be partially oxidized and could still coordinate with the Rh center via the unoxidized phosphorus atoms to stabilize the catalyst, based on the multiple chelating modes of the tetraphosphine ligand. Hence, the catalytic activity and selectivity could be retained for a certain number of runs.
Zhou, Fanding,Zhang, Lin,Wu, Qianhui,Guo, Fuya,Tang, Songbai,Xu, Bin,Yuan, Maolin,Fu, Haiyan,Li, Ruixiang,Zheng, Xueli,Chen, Hua
(2018/11/23)

Anisole: A further step to sustainable hydroformylation
Hydroformylation, also known as the "oxo" process, is a major industrial process that employs rhodium or cobalt catalysts in solution; therefore the solvent of this process is a critical issue for its sustainability. Although several innovative solutions have been proposed recently, traditional fossil-derived solvents dominate the scenario for this reaction. In this paper, we studied a series of solvents considered more sustainable in recent ranks in the hydroformylation of a series of olefins. Anisole, a solvent with an impressive sustainability rank and very scarcely exploited in hydroformylation, proved to be an excellent alternative for this reaction.
Delolo, Fábio G.,Dos Santos, Eduardo N.,Gusevskaya, Elena V.
supporting information
p. 1091 - 1098
(2019/03/12)

HYDROFORMYLATION METHOD AND CATALYST USING RHODIUM-RUTHENIUM DUAL METAL AND TETRADENTATE PHOSPHINE LIGAND
A homogeneous catalytic reaction method and a catalyst for isomerization and hydroformylation of long-chain internal olefins are disclosed. A rhodium-ruthenium metal complex is used as a catalyst; and the ligands are tetradentate phosphine ligands. By means of the catalytic system, homogeneous internal olefin isomerization aid hydroformylation can be performed under a certain temperature and pressure to obtain aldehyde products having high normal to iso ratios. The present invention is applicable to not only long-chain internal olefins (≥C8) but also internal olefins having a carbon number less than 8.
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Paragraph 0036-0037; 0039-0040

(2019/11/19)

Encapsulated liquid nano-droplets for efficient and selective biphasic hydroformylation of long-chain alkenes
Aqueous nano-droplets of homogeneous Rh-TPPTS catalyst encapsulated within the cavity of hollow silica nanospheres were fabricated for biphasic hydroformylation of long-chain alkenes, which showed significant reaction rate enhancement effects and improved aldehyde selectivity.
Zhang, Xiaoli,Wei, Juan,Zhang, Xiaoming
supporting information
p. 14134 - 14138
(2019/09/18)

Integration of phosphine ligands and ionic liquids both in structure and properties-a new strategy for separation, recovery, and recycling of homogeneous catalyst
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
p. 3583 - 3596
(2019/07/10)

Porous organic polymer supported rhodium as a reusable heterogeneous catalyst for hydroformylation of olefins
A new porous organic polymer has been prepared via copolymerization of divinyl-functionalized phosphoramidite ligand and tris(4-vinylphenyl)phosphine. The porous polymer was loaded with Rh(acac)CO2 to yield a supported Rh catalyst, which demonstrated good regioselectivity (l/b = 6.7-52.8) and high catalytic activity (TON up to 45.3 × 104) in hydroformylation of terminal and internal olefins. Remarkably, the heterogeneous catalyst can be reused at least 10 cycles without losing activity and selectivity in hydroformylation of 1-hexene.
Jia, Xiaofei,Liang, Zuyu,Chen, Jianbin,Lv, Jinhe,Zhang, Kai,Gao, Mingjie,Zong, Lingbo,Xie, Congxia
supporting information
p. 2147 - 2150
(2019/03/26)

XL-Xantphos: Design and Synthesis of a Mechanistic Probe of Xantphos O-Coordination in Catalytic Reactions
The synthesis and characterization of an analog of the Xantphos ligand that is geometrically incapable of coordination of the xanthene bridging oxygen atom is reported. This new ligand, XL-Xantphos, ((9,9-dimethyl-9H-xanthene-4,5-diyl)bis(4,1-phenylene))bis(diphenylphosphane), was studied in homogeneous, catalytic reactions for comparison with Xantphos. The XL-Xantphos ligand performed essentially identically to Xantphos in Rh-catalyzed hydroformylation of 1-octene, which suggests that the high regioselectivity for linear aldehyde is due to the large bite angle of these ligands and is not influenced by oxygen coordination to the metal. The Pd-catalyzed amidocarbonylation of 4-bromoanisole with dimethylhydroxylamine hydrochloride similarly showed no difference between Xantphos and XL-Xantphos. Computations on Pd(II) phosphine complexes at the DLPNO-CCSD(T) level of theory indicated that these ligands have different preferences for cis and trans coordination modes. The XL-Xantphos ligand has a thermodynamic preference for trans-chelated structures, whereas the cis-[(Xantphos)PdCl2] isomer was calculated to be thermodynamically more stable than its trans isomer. Given the key role of d8 square planar Pd intermediates in many catalytic cycles, the greater preference of Xantphos to form cis chelates may indeed be a factor which has made this ligand particularly effective.
Whiteker, Gregory T.,Li, Fangzheng,Froese, Robert D. J.,Tulchinsky, Michael L.,Hazari, Amaruka,Klosin, Jerzy
supporting information
p. 2233 - 2238
(2019/05/21)

Reductive-hydroformylation of 1-octene to nonanol using fibrous Co3O4 catalyst
This work reports, reductive-hydroformylation of 1-octene to nonanol in the presence of fine fibrous cobalt oxide (Co3O4) nano-catalyst prepared via urea reduction method under phosphine-free and additive free condition. Co3O4 nano-catalyst was prepared by the wet chemical method and was characterized using various instrumental techniques like FEG-SEM, EDS, XRD, TPR and FTIR. The effects of various reaction parameters such as temperature, synthesis gas (CO/H2) pressure/ratio, catalyst loading, solvent and time were studied. The reaction was successfully achieved in tetrahydrofuran (THF) as the solvent medium. This reaction believed to takes place through the generation of HCox(CO)y active catalyst species. The Co3O4 nano-catalyst could be recycled up to three consecutive cycles.
Bhagade, Sachin S.,Chaurasia, Shivkumar R.,Bhanage, Bhalchandra M.
p. 147 - 152
(2017/09/06)

Flow chemistry-enabled studies of rhodium-catalyzed hydroformylation reactions
We present an automated microscale flow chemistry platform for rapid performance evaluation of continuous and discrete reaction parameters in homogeneous hydroformylation reactions. We demonstrate the versatility of the developed microfluidic platform through a systematic study of the effects of a library of phosphine-based ligands on catalytic activity and regioselectivity.
Zhu, Cheng,Raghuvanshi, Keshav,Coley, Connor W.,Mason, Dawn,Rodgers, Jody,Janka, Mesfin E.,Abolhasani, Milad
supporting information
p. 8567 - 8570
(2018/08/06)

Dess-Martin periodinane oxidative rearrangement for preparation of α-keto thioesters
A Dess-Martin Periodinane (DMP) mediated oxidative rearrangement reaction was uncovered. The reaction proceeds via oxidation of a β-hydroxy thioester to a β-keto thioester, followed by an α-hydroxylation and then further oxidation to form a vicinal thioester tricarbonyl. This product then rearranges, extruding CO2, to form an α-keto product. The mechanism of the rearrangement was elucidated using 13C labelling and analysis of the intermediates as well as the products of the reaction. This efficient process allows for easy preparation of α-keto thioesters which are potential intermediates in the synthesis of pharmaceutically important heterocyclic scaffolds such as quinoxalinones.
Sanichar, Randy,Carroll, Ciaran,Kimmis, Ryan,Reiz, Bela,Vederas, John C.
p. 593 - 597
(2018/02/09)

Rhodium-Complex-Catalyzed Hydroformylation of Olefins with CO2and Hydrosilane
A rhodium-catalyzed one-pot hydroformylation of olefins with CO2, hydrosilane, and H2has been developed that affords the aldehydes in good chemoselectivities at low catalyst loading. Mechanistic studies indicate that the transformation is likely to proceed through a tandem sequence of poly(methylhydrosiloxane) (PMHS) mediated CO2reduction to CO and a conventional rhodium-catalyzed hydroformylation with CO/H2. The hydrosilylane-mediated reduction of CO2in preference to aldehydes was found to be crucial for the selective formation of aldehydes under the reaction conditions.
Ren, Xinyi,Zheng, Zhiyao,Zhang, Lei,Wang, Zheng,Xia, Chungu,Ding, Kuiling
supporting information
p. 310 - 313
(2016/12/30)

Tuning the Porphyrin Building Block in Self-Assembled Cages for Branched-Selective Hydroformylation of Propene
Unprecedented regioselectivity to the branched aldehyde product in the hydroformylation of propene was attained on embedding a rhodium complex in supramolecular assembly L2, formed by coordination-driven self-assembly of tris(meta-pyridyl)phosphine and zinc(II) porpholactone. The design of cage L2 is based on the ligand-template approach, in which the ligand acts as a template for cage formation. Previously, first-generation cage L1, in which zinc(II) porphyrin units were utilized instead of porpholactones, was reported. Binding studies demonstrate that the association constant for the formation of second-generation cage L2 is nearly an order of magnitude higher than that of L1. This strengthened binding allows cage L2 to remain intact in polar and industrially relevant solvents. As a consequence, the unprecedented regioselectivity for branched aldehyde products can be maintained in polar and coordinating solvents by using the second-generation assembly.
Wang, Xiaowu,Nurttila, Sandra S.,Dzik, Wojciech I.,Becker, René,Rodgers, Jody,Reek, Joost N. H.
supporting information
p. 14769 - 14777
(2017/09/06)

Ligand effects in rhodium-catalyzed hydroformylation with bisphosphines: Steric or electronic?
Twelve commercially available bisphosphine ligands have been evaluated in rhodium-catalyzed hydroformylation reactions. All ligands exhibited high chemoselectivities for aldehyde formation. The highest enantioselectivity (53% ee) of styrene hydroformylation was achieved with (S)-BTFM-Garphos (L7) substituted with electron withdrawing substituents. High pressure NMR (HP-NMR) spectroscopy and in situ high pressure IR spectroscopy (HP-IR) were used to study the resting states of the catalyst species in the reactions. The ligand effect on the structures of the observable species was examined. Both electronic and steric factors were considered to contribute to the performance of the various ligands. The results showed that decreasing the phosphine basicity increased the enantioselectivity, while in the systems studied here the steric character plays a less important role than the electronic features in achieving good regioselectivities.
Jiao, Yunzhe,Torne, Marta Serrano,Gracia, Jose,Niemantsverdriet,Van Leeuwen, Piet W. N. M.
p. 1404 - 1414
(2017/05/05)

A modular family of phosphine-phosphoramidite ligands and their hydroformylation catalysts: steric tuning impacts upon the coordination geometry of trigonal bipyramidal complexes of type [Rh(H)(CO)2(P^P?)]
Four new phosphine-phosphoramidite bidentate ligands have been synthesised and studied in rhodium-catalysed hydroformylation. Variable temperature NMR studies have been used along with HPIR to investigate the coordination mode of the trigonal bipyramidal complexes formed from [Rh(acac)(CO)2], ligand and syngas. It was found that small changes to the ligand structure have a large effect on the geometry of the active catalytic species. The rhodium catalysts of these new ligands were found to give unusually high iso-selectivity in the hydroformylation of propene and 1-octene.
How, Rebecca C.,Hembre, Robert,Ponasik, James A.,Tolleson, Ginette S.,Clarke, Matthew L.
p. 118 - 124
(2015/12/31)

First efficient catalyst recycling for the iridium-catalysed hydroformylation of 1-octene
This paper describes the development of an efficient catalyst recycling concept for the iridium-catalysed hydroformylation of 1-octene through the investigation of biphasic systems, thermomorphic solvent systems and an ex situ extraction. Particularly high selectivities (>90%) towards the desired aldehydes as well as low rates of iridium leaching were observed using the monosulfonated triphenylphosphine ligand (TPPMS). In polar solvents such as propylene carbonate or N,N-dimethylformamide, low rates of catalyst leaching (0.2%) as well as high rates of product separation (nearly 80%) were achieved. High reaction rates and a long-term activity and stability of the catalyst were observed using the solvent N,N-dimethylformamide and the extraction with non-polar solvents.
Behr,K?mper,Kuhlmann,Vorholt,Franke
p. 208 - 214
(2015/12/31)

New tetraphosphite ligands for regioselective linear hydroformylation of terminal and internal olefins
We successfully developed new tetraphosphite ligands L1-L5 and applied them to the rhodium-catalyzed hydroformylation of terminal and internal olefins. High catalytic reactivities and excellent regioselectivities for linear aldehydes were obtained in the rhodium-catalyzed hydroformylation of simple olefins (l/b ratio up to 90, 98.9% linear selectivity, 99.2% conversion) using the tetraphosphite ligand L2. And the tetraphosphite ligand L2 also displayed moderate to good linear regioselectivities for challenging substrates styrene and internal olefin 2-octene.
Zhang, Zongpeng,Chen, Caiyou,Wang, Qian,Han, Zhengyu,Dong, Xiu-Qin,Zhang, Xumu
p. 14559 - 14562
(2016/02/19)

Synthesis of phosphine-containing dipyrromethene cobalt complexes, promising ligands for homogeneous catalysis in nanomembrane reactors
Complexes of 5-(4-diphenylphosphinophenyl)dipyrromethene with trivalent cobalt (Ph2PC6H4DP)3Co (DP for dipyrromethene) were obtained for the first time, and their reaction with dicarbonylrhodium(I) acetylacetona
Leushina,Gorbunov,Cheshkov,Kuchinskaya,Anisimov,Maksimov,Terenina,Khoroshutin,Karakhanov
p. 1625 - 1631
(2017/01/28)

An Effective Pd-Catalyzed Regioselective Hydroformylation of Olefins with Formic Acid
An effective palladium-catalyzed regioselective hydroformylation of olefins with formic acid is described. The ligand plays a crucial role in directing the reaction pathway. Linear aldehydes can be obtained in up to 93% yield with >20:1 regioselectivity using 1,3-bis(diphenylphosphino)propane (dppp) as the ligand. The reaction process is operationally simple and requires no syngas.
Ren, Wenlong,Chang, Wenju,Dai, Jie,Shi, Yuan,Li, Jingfu,Shi, Yian
supporting information
p. 14864 - 14867
(2016/11/29)

Phosphonium-based aminophosphines as bifunctional ligands for sequential catalysis of one-pot hydroformylation-acetalization of olefins
A series of ionic phosphonium-based aminophosphines L1-L3 were prepared and fully characterized, in each of which the involved bifunctional moieties of the phosphine fragment and Lewis acidic phosphonium were linked together by stable chemical bonds and bridged by one N-atom. The molecular structure of the L2-ligated Rh-complex (Rh-L2) indicated that such bifunctionalities were well retained without incompatibility problems. Investigations on co-catalysis over L1-L3 showed that L3 exhibited the best sequential catalysis for both hydroformylation and acetalization. The phosphine fragment in L3 was responsible for hydroformylation together with the Rh-complex and the phosphonium acted as the Lewis acidic catalyst in charge of acetalization. The L3-Rh(acac)(CO)2 system also exhibited good generality to hydroformylation-acetalization of a wide range of olefins in different alcohols.
Wang, Peng,Liu, Huan,Li, Yong-Qi,Zhao, Xiao-Li,Lu, Yong,Liu, Ye
p. 3854 - 3861
(2016/06/14)

Co-catalysis of a bi-functional ligand containing phosphine and Lewis acidic phosphonium for hydroformylation-acetalization of olefins
A novel ionic bi-functional ligand of L2 containing a phosphine and a Lewis acidic phosphonium with I- as the counter-anion was prepared and fully characterized. The molecular structure indicated that the bi-functionalities in L2 were well retained without the incompatibility problem for quenching of the acidity of the phosphonium cation by the Lewis basic phosphine fragment or the anionic I- when the incorporated phosphine fragment and the Lewis acidic phosphonium were strictly located in the confined cis-positions. The co-catalysis over L2-Rh(acac)(CO)2 in the ways of synergetic catalysis and sequential catalysis was successfully fulfilled for one-pot hydroformylation-acetalization, which proved not to be the result of the simple mixture of the mono-phosphine (L4) and the phosphonium salt (L4′). In L2, the phosphonium not only acted as a Lewis acid organocatalyst to drive the sequential acetalization of aldehydes, but also contributed to the synergetic catalysis for the preceding hydroformylation through stabilizing the Rh-acyl intermediate with the phosphine cooperatively. The L2-Rh(acac)(CO)2 system is also generally applied to hydroformylation-acetalization of a wide range of olefins in different alcohols. Advantageously, as an ionic phosphonium-based ligand, L2 could be recycled for 7 runs with Rh(acac)(CO)2 together in RTIL of [Bmim]BF4 without obvious activity loss or metal leaching.
Li, Yong-Qi,Wang, Peng,Liu, Huan,Lu, Yong,Zhao, Xiao-Li,Liu, Ye
p. 1798 - 1806
(2016/04/01)

Process for the catalytic production of unsaturated aldehydes
The invention concerns a process for the catalytic production of unsaturated aldehydes by reacting an olefin in the presence of carbon monoxide and hydrogen, a rhodium compound and organic phosphorus-containing ligands in an organic solvent as well as a co-catalyst formed from a weak organic acid and an organic amine.
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Page/Page column 12

(2016/02/05)

Method for highly selective preparation of linear aldehyde by olefin two-phase hydroformylation based on phosphine functionalized polyether alkyl guanidine salt ionic liquid
The invention relates to a method for highly selective preparation of linear aldehyde by olefin two-phase hydroformylation based on a phosphine functionalized polyether alkyl guanidine salt ionic liquid. The method adopts a two-phase catalytic system, the catalytic system is composed of the phosphine functionalized polyether alkyl guanidine salt ionic liquid, a polyether alkyl guanidine salt ionic liquid, a rhodium catalyst, a reaction substrate olefin and a reaction product aldehyde, liquid/liquid two-phase hydroformylation reaction is carried out under certain reaction temperature and synthesis gas pressure, simple two-phase separation is carried out at the end of the reaction to realize separation and circulation of the rhodium catalyst, the rhodium catalyst can be used repeatedly, and the catalytic activity and selectivity do not decrease significantly. The TOF value of the system reaches 300-3400h, and the catalytic cycle cumulative TON value reaches 30832.
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Paragraph 0040; 0041; 0042

(2017/01/02)

Method of preparing normal aldehyde in highly selective manner through olefin two-phase hydroformylation on basis of phosphine functionalized polyether quaternary phosphorus salt ion liquid
The invention relates to a method of preparing normal aldehyde in a highly selective manner through olefin two-phase hydroformylation on the basis of phosphine functionalized polyether pyrrolidine salt ion liquid. The method includes: adopting a two-phase catalysis system which is composed of phosphine functionalized polyether quaternary phosphorus salt ion liquid, rhodium catalyst, 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, separation 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 300-2800 h, catalytic circulating accumulated TON value reaches 30856.
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Paragraph 0075-0077

(2017/03/14)

Method for high-selectivity preparation of normal aldehyde through olefin two-phase hydroformylation on basis of phosphine-functionalized polyether imidazolium salt ionic liquid
The invention relates to a method for high-selectivity preparation of normal aldehyde through olefin two-phase hydroformylation on the basis of a phosphine-functionalized polyether imidazolium salt ionic liquid. According to the method, a two-phase catalytic system is adopted, the catalytic system comprises a phosphine-functionalized polyether imidazolium salt ionic liquid, a polyether imidazolium salt ionic liquid, a rhodium catalyst, 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, the rhodium catalyst is separated and cycled through simple two-phase separation after the reaction ends, the rhodium catalyst can be recycled multiple times, and the catalytic activity and the selectivity are not remarkably reduced. The TOF value of the system reaches 400-3,300 h and the catalytic cycle accumulated TON value reaches 33,975.
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Paragraph 0051; 0079; 0080; 0081

(2017/11/17)

Highly efficient heterogeneous hydroformylation over rh-metalated porous organic polymers: Synergistic effect of high ligand concentration and flexible framework
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
supporting information
p. 5204 - 5209
(2015/05/05)

Synthesis of a bimetallic P-N bridged rhodium (I)-ruthenium (II) complex: Application in the hydroformylation reaction
The reaction of [Rh(acac)(PPh2Py)2] (acac = acetylacetonate, PPh2Py = 2-(diphenylphosphino)pyridine) with [Cp?Ru(CH3CN)3][OTf] (Cp? = pentamethylcyclopentadienyl, OTf = trifluoromethanesulfonate) provides a cationic bimetallic complex [Cp?Ru(PPh2Py)2Rh(acac)][OTf], in which a ruthenium-rhodium coordinate (dative covalent) bond is formed. The structure was ascertained by single crystal X-ray diffraction. The catalytic performances of the bimetallic complex were evaluated in the hydroformylation reaction of 1-octene and compared to those of the in situ formed catalysts and the mononuclear counterparts. The catalysis results point out that the bimetallic complex is fragmenting under hydroformylation conditions, which was confirmed by NMR analysis.
Kartashova, Ksenia,Mallet-Ladeira, Sonia,Axet, M. Rosa
p. 226 - 231
(2015/11/02)

Crucial role of additives in iridium-catalyzed hydroformylation
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
p. 243 - 248
(2015/09/01)

Advantages of the solventless hydroformylation of olefins
Abstract The hydroformylation of olefins using Rh(acac)(CO)2 as a catalyst with the excess of PPh3 was investigated at the temperature of 80°C within the pressure range from 4 to 12 bar in a neat substrate, without a solvent. The conversion of 1-hexene was complete, with a linear-to-branched aldehyde ratio of ca. 10. Very good results were also obtained for 1-pentene and 1-octene. The catalytic performance of the Rh(acac)(CO)2/PPh3 catalytic system in hydroformylation under solventless conditions was better than that in toluene, owing to the high concentration of the reactants. Recycling experiments confirmed the good stability of the catalyst and its constant activity.
Alsalahi,Trzeciak
p. 147 - 151
(2015/08/18)

Understanding Programming of Fungal Iterative Polyketide Synthases: The Biochemical Basis for Regioselectivity by the Methyltransferase Domain in the Lovastatin Megasynthase
Highly reducing polyketide synthases (HR-PKSs) from fungi synthesize complex natural products using a single set of domains in a highly programmed, iterative fashion. The most enigmatic feature of HR-PKSs is how tailoring domains function selectively during different iterations of chain elongation to afford structural diversity. Using the lovastatin nonaketide synthase LovB as a model system and a variety of acyl substrates, we characterized the substrate specificity of the LovB methyltransferase (MT) domain. We showed that, while the MT domain displays methylation activity toward different β-ketoacyl groups, it is exceptionally selective toward its naturally programmed β-keto-dienyltetraketide substrate with respect to both chain length and functionalization. Accompanying characterization of the ketoreductase (KR) domain displays broader substrate specificity toward different β-ketoacyl groups. Our studies indicate that selective modifications by tailoring domains, such as the MTs, are achieved by higher kinetic efficiency on a particular substrate relative to the rate of transformation by other competing domains.
Cacho, Ralph A.,Thuss, Justin,Xu, Wei,Sanichar, Randy,Gao, Zhizeng,Nguyen, Allison,Vederas, John C.,Tang, Yi
p. 15688 - 15691
(2016/01/09)

Efficient Domino Hydroformylation/Benzoin Condensation: Highly Selective Synthesis of α-Hydroxy Ketones
An improved domino hydroformylation/benzoin condensation to give α-hydroxy ketones has been developed. Easily available olefins are smoothly converted into the corresponding α-hydroxy ketones in high yields with excellent regioselectivities. Key to success is the use of a specific catalytic system consisting of a rhodium/phosphine complex and the CO2 adduct of an N-heterocyclic carbene. 2 for 1: An improved domino hydroformylation/benzoin condensation of olefins has been developed in the presence of a specific catalytic system consisting of a rhodium/phosphine complex and the CO2 adduct of an N-heterocyclic carbene.
Dong, Kaiwu,Sang, Rui,Soule, Jean-Francois,Bruneau, Christian,Franke, Robert,Jackstell, Ralf,Beller, Matthias
supporting information
p. 18033 - 18037
(2015/12/24)

Molybdenum carbonyl grafted onto silicate intercalated cobalt-aluminum hydrotalcite: A new potential catalyst for the hydroformylation of octene
We present the first example of molybdenum carbonyl grafted on diaminosiloxane-functionalized cobalt-aluminum hydrotalcite (CA-HTSi-DA-Mo) as a promising catalyst for the hydroformylation of olefins. The catalyst showed 80% conversion with selective formation of branched aldehyde. About 70% of the catalytic activity retains even after three cycles.
Sakthivel, Ayyamperumal,Mahato, Nihar Ranjan,Baskaran, Thangaraj,Christopher, Jayaraj
p. 55 - 61
(2015/04/27)

Recoverable and recyclable water-soluble sulphonated salicylaldimine Rh(i) complexes for 1-octene hydroformylation in aqueous biphasic media
A series of water-soluble Rh(i) mononuclear complexes of general formula: [Rh(sulphsal-X-R)(COD)] [sulphsal = sulphonated salicylaldimine, COD = cyclooctadiene; where R = H, Cl, CH3 and X = H, tBu] have been synthesized. All the compounds were characterised using various spectroscopic and analytical techniques such as nuclear magnetic resonance spectroscopy, infrared spectroscopy, single crystal X-ray diffraction (for complex 10) and mass spectrometry. All the compounds display excellent water-solubility at room temperature and were tested as catalyst precursors in the aqueous biphasic hydroformylation of 1-octene. The catalysts could be easily recovered by phase separation and were used up to 5 times without any significant loss in activity and 1-octene conversion. Very high yields of the expected aldehydes were obtained without addition of any phase transfer agents, co-solvents or hydrophobic ligands. Excellent aldehyde chemoselectivity is observed for all the catalysts but this varied each time the catalysts were recycled, with the formation of a small amount of internal olefins. ICP-OES and mercury poisoning experiments show that a combination of homogeneous catalysis and catalysis mediated by nanoparticles is taking place in these systems. This journal is
Matsinha, Leah C.,Mapolie, Selwyn F.,Smith, Gregory S.
p. 1240 - 1248
(2015/02/18)

From alkenes to alcohols by cobalt-catalyzed hydroformylation-reduction
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
supporting information
p. 1241 - 1246
(2015/03/05)

A new biogenerated Rh-based catalyst for aqueous biphasic hydroformylation
A new bio-generated rhodium based system embedded in a peculiar polysaccharide matrix (Rh-EPS), was obtained and purified from cultures of bacterial cells of Klebsiella oxytoca DSM 29614. The product was analyzed with different techniques to obtain information on its structure-property correlation. In order to determine its catalytic activity and selectivity in the aqueous biphasic hydroformylation some olefins were chosen as model substrates, obtaining fine-good results.
Paganelli, Stefano,Piccolo, Oreste,Baldi, Franco,Gallo, Michele,Tassini, Riccardo,Rancan, Marzio,Armelao, Lidia
p. 32 - 36
(2015/09/01)

Tandem hydroformylation-acetalization with a ruthenium catalyst immobilized in ionic liquids
For the first time, a ruthenium catalyzed hydroformylation-acetalization reaction of olefins is presented. The tandem reaction proceeds well with 1,2- or 1,3-diols, trapping the intermediary formed aldehydes as cyclic acetals. In this manner the hydrogenation of the aldehydes to the corresponding alcohols usually observed with Ru catalysts is prevented. The optimized catalytic system consisting of Ru catalyst, ionic liquids, acetic acid and ammonium salt can be recycled and reused for at least two further runs. Interestingly, styrenes as substrate give preferentially terminal acetals.
Norinder, Jakob,Rodrigues, Claudia,B?rner, Armin
p. 139 - 143
(2014/05/20)

METHOD FOR HYDROFORMYLATION OF UNSATURATED COMPOUNDS
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 0073

(2014/02/16)

Highly active hydroformylation catalysts: Synthesis, characterisation and catalytic performance
The phoszone ligand [(Ph2P)(bis-3,5-CF3-Ph)]NN= CH(penta-fluoro-Ph) transformed in liquid CO2 at room temperature in presence of [Rh(cod)2]OTf into [Rh(cod)(η2-P,P′- Ph2POPPh2)]OTf. Replacing the O-atom in Ph 2POPPh2 by a PrN-group leads to the ligand PrN(PPh 2)2 acting similarly as a bidentate ligand in [Rh(cod)(η2-P,P′-PrN(PPh2)2)]OTf. Hydroformylation of 1-octene with in situ catalysts formed by the ligands with [Rh(cod)2]OTf showed hydroformylation activities at 50 % conversion of 16,000 h-1 (PrN(PPh2)2/[Rh(cod) 2]OTf) and 24,000 h-1 (phoszone/[Rh(cod)2]OTf), respectively.
Piras, Elisabetta,Powietzka, Bernhard,Wurst, Frederik,Neumann-Walter, Doreen,Gruetzmacher, Hans-Joerg,Otto, Thomas,Zevaco, Thomas,Walter, Olaf
p. 673 - 680
(2013/07/26)

Preparation of phosphine-functionalized polystyrene stars by metal catalyzed controlled radical copolymerization and their application to hydroformylation catalysis
Well defined star copolymers have been prepared by copper-catalyzed atom transfer radical copolymerization of styrene and styryldiphenylphosphine starting from a modified Boltorn H30 multifunctional initiator. These polymers and an analogue obtained by debromination of the arm ends with nBu 3SnH have been used in combination with [Rh(acac)(CO)2] for the homogeneous phase hydroformylation of 1-octene.
Cardozo, Andres F.,Manoury, Eric,Julcour, Carine,Blanco, Jean-Francois,Delmas, Henri,Gayet, Florence,Poli, Rinaldo
p. 9148 - 9156
(2013/07/27)

From olefins to alcohols: Efficient and regioselective ruthenium-catalyzed domino hydroformylation/reduction sequence
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
supporting information
p. 2949 - 2953
(2013/04/10)

Novel spiroketal-based diphosphite ligands for hydroformylation of terminal and internal olefins
Spiroketal-based diphosphite ligands have been developed for the rhodium-catalyzed hydroformylation reaction. Under the optimized reaction conditions, a turnover number (TON) of up to 2.4 × 104 and a linear to branched ratio (l/b) of up to 93 were obtained in the hydroformylation of terminal olefins. The catalysts were also found to be effective in the isomerization-hydroformylation of some internal olefins.
Jia, Xiaofei,Wang, Zheng,Xia, Chungu,Ding, Kuiling
p. 1901 - 1904
(2013/07/26)

A novel triphosphoramidite ligand for highly regioselective linear hydroformylation of terminal and internal olefins
The first triphosphorus ligand has been designed and synthesized for highly regioselective linear hydroformylations. A very high l/b ratio (up to 471, 99.8% linear selectivity) was obtained in the linear hydroformylation of representative terminal and internal olefins. For the range of substrates tested, the regioselectivities achieved utilizing the novel triphosphoramidite ligand were much better than those of the bisphosphoramidite ligand and close to those of the tetraphosphoramidite ligand.
Chen, Caiyou,Qiao, Yu,Geng, Huiling,Zhang, Xumu
supporting information
p. 1048 - 1051
(2013/04/24)

A selective functionalized mesoporous silica-supported Rh catalyst for effective 1-octene hydroformylation
Through different functionalization methods, three kinds of Rh-immobilized mesoporous silicas have successfully been prepared to investigate catalytic behavior, including yield and the linear/branched ratio of aldehyde (L/B) in 1-octene hydroformylation. A conventional post grafting method and two kinds of selective bifunctionalized methods for modification of the mesoporous silica have been applied for this purpose. A relatively high L/B (>2.0) was effectively achieved using Rh-immobilized inner pores in the MCM-41 support due to the confinement effects of the Rh complex in the nanospace. Moreover, the Rh-immobilized MCM-41 catalyst, passivated with trimethylchlorosilane (TMCS) only on the external surface, showed fairly good yields of the aldehyde (>40%). Copyright
Jeon, Jong-Ki,Ko, Young Soo,Yim, Jin-Heong
p. 3087 - 3095
(2013/08/25)

Water-soluble-phosphines-assisted cobalt separation in cobalt-catalyzed hydroformylation
The hydroformylation of octene-1 and the removal of Co2(CO) 8 and HCo(CO)4 from the reaction products including commercial C9 OXO-product were studied under biphasic conditions using an aqueous solution of different electr
Mika, Laszlo T.,Orha, Laszlo,Van Driessche, Eddie,Garton, Ron,Zih-Perenyi, Katalin,Horvath, Istvan T.
p. 5326 - 5332
(2013/11/06)

Chemo- and regioselective homogeneous rhodium-catalyzed hydroamidomethylation of terminal alkenes to N-alkylamides
A rhodium/xantphos homogeneous catalyst system has been developed for direct chemo- and regioselective mono-N-alkylation of primary amides with 1-alkenes and syngas through catalytic hydroamidomethylation with 1-pentene and acetamide as model substrates. For appropriate catalyst performance, it appears to be essential that catalytic amounts of a strong acid promoter, such as p-toluenesulfonic acid (HOTs), as well as larger amounts of a weakly acidic protic promoter, particularly hexafluoroisopropyl alcohol (HORF) are applied. Apart from the product N-1-hexylacetamide, the isomeric unsaturated intermediates, hexanol and higher mass byproducts, as well as the corresponding isomeric branched products, can be formed. Under optimized conditions, almost full alkene conversion can be achieved with more than 80 % selectivity to the product N-1-hexylamide. Interestingly, in the presence of a relatively high concentration of HORF, the same catalyst system shows a remarkably high selectivity for the formation of hexanol from 1-pentene with syngas, thus presenting a unique example of a selective rhodium-catalyzed hydroformylation-hydrogenation tandem reaction under mild conditions. Time-dependent product formation during hydroamidomethylation batch experiments provides evidence for aldehyde and unsaturated intermediates; this clearly indicates the three-step hydroformylation/condensation/hydrogenation reaction sequence that takes place in hydroamidomethylation. One likely role of the weakly acidic protic promoter, HORF, in combination with the strong acid HOTs, is to establish a dual-functionality rhodium catalyst system comprised of a neutral rhodium(I) hydroformylation catalyst species and a cationic rhodium(III) complex capable of selectively reducing the imide and/or ene-amide intermediates that are in a dynamic, acid-catalyzed condensation equilibrium with the aldehyde and amide in a syngas environment. Taking control: A rhodium/xantphos homogeneous catalyst system has been developed for direct chemo- and regioselective mono-N-alkylation of primary amides with 1-alkenes and syngas through the new catalytic hydroamidomethylation reaction (see picture). Copyright
Raoufmoghaddam, Saeed,Drent, Eite,Bouwman, Elisabeth
p. 1759 - 1773
(2013/10/21)