- An efficient and ultrastable single-Rh-site catalyst on a porous organic polymer for heterogeneous hydrocarboxylation of olefins
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A heterogeneous hydrocarboxylation process of olefins to obtain carboxylic acids with one more carbon was first realized using a single-Rh-site catalyst formed on porous organic polymer (Rh1/POPs). The in situ formation of hydrophilic porous ionic polymer from hydrophobic POPs with the help of CH3I led to high activity and superb stability.
- Yuan, Qiao,Song, Xiangen,Feng, Siquan,Jiang, Miao,Yan, Li,Li, Jingwei,Ding, Yunjie
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supporting information
p. 472 - 475
(2021/01/25)
-
- Hydroxycarbonylation of alkenes with formic acid using a rhodium iodide complex and alkyl ammonium iodide
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Hydroxycarbonylation of alkenes using formic acid (HCOOH) is ideal for the synthesis of various carboxylic acids as a means to develop a sustainable reaction system with lower environmental impact. In this study, we developed a new catalytic system for hydroxycarbonylation of alkenes with HCOOH using a Vaska-type Rh complex with an iodide ligand, RhI(CO)(PPh3)2(1), as the catalyst, and a quaternary ammonium iodide salt as the promoter for the catalyst. In comparison with similar reaction systems using Rh catalysts, our reaction system is safer and more environmentally friendly since it does not require high-pressure conditions, explosive gases, or environmentally unfriendly CH3I and extra PPh3promoters. In addition, we also experimentally clarified that the catalytic reaction proceedsviaRhHI2(CO)(PPh3)2(2), which is formed by the reaction of1with a quaternary ammonium iodide salt andp-TsOH. Furthermore, the Rh(iii) complex2can catalyze hydroxycarbonylation of alkenes with HCOOH without any promoters.
- Okada, Masaki,Takeuchi, Katsuhiko,Matsumoto, Kazuhiro,Oku, Tomoharu,Choi, Jun-Chul
-
supporting information
p. 8727 - 8734
(2021/10/22)
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- Ruthenium-catalysed hydroxycarbonylation of olefins
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State-of-the-art catalyst systems for hydroxy- and alkoxycarbonylations of olefins make use of palladium complexes. In this work, we report a complementary ruthenium-catalysed hydroxycarbonylation of olefins applying an inexpensive Ru-precursor (Ru3(CO)12) and PCy3as a ligand. Crucial for the success of this transformation is the use of hexafluoroisopropanol (HFIP) as the solvent in the presence of an acid co-catalyst (PTSA). Overall, moderate to good yields are obtained using aliphatic olefins including the industrially relevant substrate di-isobutene. This atom-efficient catalytic transformation provides straightforward access to various carboxylic acids from unfunctionalized olefins.
- Dühren, Ricarda,Kucmierczyk, Peter,Jackstell, Ralf,Franke, Robert,Beller, Matthias
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p. 2026 - 2030
(2021/04/09)
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- Synthesis of Carboxylic Acids by Palladium-Catalyzed Hydroxycarbonylation
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The synthesis of carboxylic acids is of fundamental importance in the chemical industry and the corresponding products find numerous applications for polymers, cosmetics, pharmaceuticals, agrochemicals, and other manufactured chemicals. Although hydroxycarbonylations of olefins have been known for more than 60 years, currently known catalyst systems for this transformation do not fulfill industrial requirements, for example, stability. Presented herein for the first time is an aqueous-phase protocol that allows conversion of various olefins, including sterically hindered and demanding tetra-, tri-, and 1,1-disubstituted systems, as well as terminal alkenes, into the corresponding carboxylic acids in excellent yields. The outstanding stability of the catalyst system (26 recycling runs in 32 days without measurable loss of activity), is showcased in the preparation of an industrially relevant fatty acid. Key-to-success is the use of a built-in-base ligand under acidic aqueous conditions. This catalytic system is expected to provide a basis for new cost-competitive processes for the industrial production of carboxylic acids.
- Sang, Rui,Kucmierczyk, Peter,Dühren, Ricarda,Razzaq, Rauf,Dong, Kaiwu,Liu, Jie,Franke, Robert,Jackstell, Ralf,Beller, Matthias
-
supporting information
p. 14365 - 14373
(2019/09/06)
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- Mild C-H functionalization of alkanes catalyzed by bioinspired copper(ii) cores
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Three new copper(ii) coordination compounds formulated as [Cu(H1.5bdea)2](hba)·2H2O (1), [Cu2(μ-Hbdea)2(aca)2]·4H2O (2), and [Cu2(μ-Hbdea)2(μ-bdca)]n (3) were generated by aqueous medium self-assembly synthesis from Cu(NO3)2, N-butyldiethanolamine (H2bdea) as a main N,O-chelating building block and different carboxylic acids [4-hydroxybenzoic (Hhba), 9-anthracenecarboxylic (Haca), or 4,4′-biphenyldicarboxylic (H2bdca) acid] as supporting carboxylate ligands. The structures of products range from discrete mono- (1) or dicopper(ii) (2) cores to a 1D coordination polymer (3), and widen a family of copper(ii) coordination compounds derived from H2bdea. The obtained compounds were applied as bioinspired homogeneous catalysts for the mild C-H functionalization of saturated hydrocarbons (cyclic and linear C5-C8 alkanes). Two model catalytic reactions were explored, namely the oxidation of hydrocarbons with H2O2 to a mixture of alcohols and ketones, and the carboxylation of alkanes with CO/S2O82- to carboxylic acids. Both processes proceed under mild conditions with a high efficiency and the effects of different parameters (e.g., reaction time and presence of acid promoter, amount of catalyst and solvent composition, substrate scope and selectivity features) were studied and discussed in detail. In particular, an interesting promoting effect of water was unveiled in the oxidation of cyclohexane that is especially remarkable in the reaction catalyzed by 3, thus allowing a potential use of diluted, in situ generated solutions of hydrogen peroxide. Moreover, the obtained values of product yields (up to 41% based on alkane substrate) are very high when dealing with the C-H functionalization of saturated hydrocarbons and the mild conditions of these catalytic reactions (50-60 °C, H2O/CH3CN medium). This study thus contributes to an important field of alkane functionalization and provides a notable example of new Cu-based catalytic systems that can be easily generated by self-assembly from simple and low-cost chemicals.
- Kirillova, Marina V.,Fernandes, Tiago A.,André, Vania,Kirillov, Alexander M.
-
supporting information
p. 7706 - 7714
(2019/08/30)
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- Regioselectivity inversion tuned by iron(iii) salts in palladium-catalyzed carbonylations
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Impactful regioselectivity control is crucial for cost-effective chemical synthesis. By using cheap and abundant iron(iii) salts, the hydroxycarbonylations of both aromatic and aliphatic alkenes were significantly enhanced in both reactivity and selectivity (iso/n or n/iso up to >99:1). Moreover, Pd-catalyzed carbonylation selectivity can be switched from branched to linear by using different Fe(iii) salts. In addition, similar results were obtained for the carbonylation of secondary alcohols.
- Huang, Zijun,Cheng, Yazhe,Chen, Xipeng,Wang, Hui-Fang,Du, Chen-Xia,Li, Yuehui
-
supporting information
p. 3967 - 3970
(2018/04/23)
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- Three-component 1D and 2D metal phosphonates: structural variability, topological analysis and catalytic hydrocarboxylation of alkanes
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Herein, we report the use of diphosphonate building blocks and chelating auxiliary N,N-ligands to generate novel polymeric architectures. Specifically, we report new 1D and 2D coordination polymers incorporating three components: transition metal ions (Co2+, Cu2+, Mn2+ or Zn2+), diphosphonate ligands (methane-diphosphonate, MDPA, or 1,2-ethanediphosphonate, EDPA) and N,N-heterocyclic chelators (1,10-phenanthroline, phen, or 2,2′-bipyridine, bpy). Six compounds were isolated under mild synthesis (ambient temperature) conditions: [Cu2(phen)2(EDPA)2(H2O)4]∞ (1), [Co(phen)(EDPA)(H2O)2]∞ (1a), {[Cu(phen)(MDPA)]·H2O]}∞ (2), [Mn(bpy)(EDPA)(H2O)2]∞ (3), [Zn(bpy)(EDPA)]∞ (4), and, lastly, a discrete Ni2+ molecular derivative [Ni(phen)(H2O)4](EDPA) (5). Synthetic details, crystal structures, and intermolecular interactions (π-π stacking and hydrogen bonding) in 1-5 are discussed. Topological analyses and classification of the underlying metal-organic networks in 1-4 were performed, revealing the uninodal 1D chains with the 2C1 topology in 1-3 and the binodal 2D layers with the 3,4L13 topology in 4. In 1-3 and 5, multiple hydrogen bonds lead to the extension of the structures to give 3D H-bonded nets with the seh-4,6-C2/c topology in 1 and 3, 2D H-bonded layers with the 3,5L52 topology in 2, and a 3D H-bonded net with the 6,6T1 topology in 5. The catalytic activity of compounds 1 and 1a was evaluated in a single-step hydrocarboxylation of cyclic and linear C5-C8 alkanes to furnish the carboxylic acids with one more carbon atom. These reactions proceed in the presence of CO, K2S2O8, and H2O at 60 °C in MeCN/H2O medium. Compound 1 showed higher activity than 1a and was studied in detail. Substrate scope was investigated, revealing that cyclohexane and n-pentane are the most reactive among the cyclic and linear C5-C8 alkanes, and resulting in the total yields of carboxylic acids (based on substrate) of up to 43 and 36%, respectively. In the case of cycloalkane substrates, only one cycloalkanecarboxylic acid is produced, whereas a series of isomeric monocarboxylic acids is generated when using linear alkanes; an increased regioselectivity at the C(2) position of the hydrocarbon chain was also observed.
- Demadis, Konstantinos D.,Anagnostou, Zafeiria,Panera, Aggeliki,Mezei, Gellert,Kirillova, Marina V.,Kirillov, Alexander M.
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p. 17788 - 17799
(2017/03/30)
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- Structurally well-characterized new multinuclear Cu(II) and Zn(II) clusters: X-ray crystallography, theoretical studies, and applications in catalysis
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Two new trinuclear Cu(ii) and dinuclear Zn(ii) clusters are crystallized out by reacting the metal salts with the triethanolamine (H3tea) ligand in the presence of benzoic acid (Hba). The complexes are characterized by elemental, thermal, magnetic, spectral (FTIR, UV-Visible, EPR, and photoluminescence) and single crystal X-ray studies. Single crystal X-ray crystallography reveals the composition of the complexes to be [Cu3(H2tea)2(ba)2(NO3)2] (1) and [Zn2(H2tea)(ba)3]H2O (2). FTIR ascertains the binding modes of H2tea-, ba- and NO3-. Triethanolamine binds in both the complexes in the monoanionic (H2tea-) mode. ba- is present as an anchoring auxiliary to generate di- and trinuclear clusters. The Cu(ii) ion is present as a distorted octahedral center in the Cu3 cluster (1), while the two Zn(ii) ions in 2 have been reported for the first time to possess distorted octahedral as well as tetrahedral geometry in the same molecule. The intriguing features of the non-covalent supramolecular interactions have been investigated and supported theoretically by using Hirshfeld surface analysis and ab initio methods. The solid state photoluminescence (PL) spectra of 1 and 2 disclose the luminescence property of the complexes. Due to the closed or nearly closed shell configuration (d9 or d10), the present complexes are screened for catalytic properties in the hydrocarboxylation of alkanes and cycloalkanes. The catalytic activity data are indicative of the potential catalytic properties of 1 and 2.
- Ansari, Istikhar A.,Sama, Farasha,Raizada, Mukul,Shahid,Ahmad, Musheer,Siddiqi, Zafar A.
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supporting information
p. 9840 - 9852
(2016/11/11)
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- Biocatalytic Characterization of Human FMO5: Unearthing Baeyer-Villiger Reactions in Humans
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Flavin-containing mono-oxygenases are known as potent drug-metabolizing enzymes, providing complementary functions to the well-investigated cytochrome P450 mono-oxygenases. While human FMO isoforms are typically involved in the oxidation of soft nucleophiles, the biocatalytic activity of human FMO5 (along its physiological role) has long remained unexplored. In this study, we demonstrate the atypical in vitro activity of human FMO5 as a Baeyer-Villiger mono-oxygenase on a broad range of substrates, revealing the first example to date of a human protein catalyzing such reactions. The isolated and purified protein was active on diverse carbonyl compounds, whereas soft nucleophiles were mostly non- or poorly reactive. The absence of the typical characteristic sequence motifs sets human FMO5 apart from all characterized Baeyer-Villiger mono-oxygenases so far. These findings open new perspectives in human oxidative metabolism.
- Fiorentini, Filippo,Geier, Martina,Binda, Claudia,Winkler, Margit,Faber, Kurt,Hall, Mélanie,Mattevi, Andrea
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p. 1039 - 1048
(2016/05/19)
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- Synthesis of Enantiomerically Enriched 2-Hydroxymethylalkanoic Acids by Oxidative Desymmetrisation of Achiral 1,3-Diols Mediated by Acetobacter aceti
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The stereoselective desymmetrisation of achiral 2-alkyl-1,3-diols is performed by oxidation of one of the two enantiotopic primary alcohol moieties by means of Acetobacter aceti MIM 2000/28 to afford the corresponding chiral 2-hydroxymethyl alkanoic acids (up to 94 % ee). The procedure, carried out in aqueous medium under mild conditions of pH, temperature and pressure, contributes to enlarge the portfolio of enzymatic oxidations available to organic chemists for the development of sustainable manufacturing processes.
- Brenna, Elisabetta,Cannavale, Flavia,Crotti, Michele,De Vitis, Valerio,Gatti, Francesco G.,Migliazza, Gaia,Molinari, Francesco,Parmeggiani, Fabio,Romano, Diego,Santangelo, Sara
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p. 3796 - 3803
(2016/12/24)
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- Hydrocarboxylation of olefins by supported aqueous-phase catalysis
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Pd-TPPTS complexes supported on acidic macro-porous resins (Pd-TPPTS/resin) have been employed for the hydrocarboxylation of 1-hexene and styrene derivatives by supported aqueous phase catalysis (SAPC). Acidic macroporous resins acted as substitutes for both heterogeneous acids and supports of Pd-TPPTS complexes afforded many advantages, such as easy separation from organic products and good reusability. The prepared Pd-TPPTS/resin catalysts were characterized by FT-IR, TG, SEM and N2 physisorption, which demonstrated that the Pd-TPPTS complexes were loaded on the resin. Compared with homogeneous analogue, the present SAP catalyst offered higher total acid yield and selectivity towards linear acid in the hydrocarboxylation of 1-hexene. Moreover, it was found that water had a significant influence on the catalytic activity and selectivity toward linear acid over the SAP catalyst. Optimum water/resin ratio at about 66.7% in the SAP catalyst afforded maximum activity under the given reaction temperature. The present SAP catalyst was highly Pd-leaching resistant and can be reused at least four times without obvious loss in activity.
- He, Zhenhong,Hou, Zhenshan,Zhang, Yagang,Wang, Tianfu,Dilixiati, Yierxiati,Eli, Wumanjiang
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p. 147 - 154
(2015/03/30)
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- Unactivated C(sp3)-H hydroxylation through palladium catalysis with H2O as the oxygen source
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A novel palladium catalyzed hydroxylation of unactivated aliphatic C(sp3)-H bonds was successfully developed. Different from conventional methods, water serves as the hydroxyl group source in the reaction. This new reaction demonstrates good reactivity and broad functional group tolerance. The C-H hydroxylated products can be readily transformed into various highly valuable chemicals via known transformations. Based on experimental and theoretical studies, a mechanism involving the Pd(ii)/(iv) pathway is proposed for this hydroxylation reaction.
- Hu, Jiantao,Lan, Tianlong,Sun, Yihua,Chen, Hui,Yao, Jiannian,Rao, Yu
-
supporting information
p. 14929 - 14932
(2015/10/06)
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- Palladium Complexes with Bulky Diphosphine Ligands as Highly Selective Catalysts for the Synthesis of (Bio-) Adipic Acid from Pentenoic Acid Mixtures.
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A series of sterically bulky diphosphines have been prepared, including P2 = trans-1,2-bis[(di-tert-butylphosphino)methyl]cyclohexane (4), (2-methylenepropane-1,3-diyl)bis(di-tert-butylphosphine) (5), bis[(di-tert-butylphosphino)methyl]dimethylsilane (6), and cis- and trans-11,12-bis[(di-tert-butylphosphino)methyl]-9,10-dihydro-9,10-ethanoanthracene (10 and 11). The corresponding palladium complexes of these ligands, P2Pd(CF3CO2)2, have been synthesized and characterized. The solid-state structures of [Pd(4)(CF3CO2)2], [Pd(5)(CF3CO2)2], [Pd(6)(CF3CO2)2], and [Pd(11)(CF3CO2)2] were obtained by single-crystal X-ray diffraction and confirm the bidentate binding mode of the ligand and a square-planar coordination geometry with a minor distortion from the ideal. The diphosphines in combination with Pd(OAc)2 have been applied in the hydroxycarbonylation of a mixture of pentenoic acid isomers to produce adipic acid with high selectivity (in several cases >95%). The (regio)selectivity of the hydroxycarbonylation reaction is highly dependent on the P2 diphosphine ligand structure, particularly the steric bulk of the substituents on the diphosphine donor and the P-Pd-P bite angle in the complexes, with respectively tertiary alkyl phosphine substituents (tert-butyl, adamantyl) and a C4 backbone P-Pd-P bite angle >100° being the common features of highly adipic acid selective systems. It is suggested that the regioselectivity of hydroxycarbonylation becomes largely driven by the chelation of the carboxylic acid functionality of pentenoic acid substrates, when smaller size P substituents and/or when P2 ligands with smaller bite angles (100°) are applied.
- Low, Choon Heng,Nobbs, James D.,Van Meurs, Martin,Stubbs, Ludger P.,Drent, Eite,Aitipamula, Srinivasulu,Pung, Michelle H. L.
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p. 4281 - 4292
(2015/09/22)
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- How to force a classical chelating ligand to a metal non-chelating bridge: The observation of a rare coordination mode of diethanolamine in the 1D complex {[Cu2(Piv)4(H3tBuDea)](Piv)}n
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The novel chain coordination polymer {[Cu2(Piv) 4(H3tBuDea)](Piv)}n (1) has been prepared through the self-assembly reaction of copper(ii) nitrate with pivalic acid (HPiv) and N-tert-butyldiethanolamine (H2tBuDea) in acetonitrile solution. Crystallographic analysis revealed the extremely rare non-chelating bridging coordination mode of diethanolamine ligand in 1, observed for the first time in transition metal complexes, as well as in complexes of diethanolamine having a non-coordinating aliphatic group at the N atom. Possible reasons for such a coordination and analysis of the main coordination modes of diethanolamine-based ligands are discussed. Variableerature (1.8-300 K) magnetic susceptibility measurements showed that 1 represents a rare example of dicopper(ii) tetracarboxylate that is a diamagnetic solid at room temperature. This behaviour is compared with literature examples and discussed on the basis of DFT calculations. Furthermore, 1 acts as an efficient catalyst for the mild hydrocarboxylation of linear and cyclic C5-C8 alkanes into the corresponding carboxylic acids.
- Nesterova, Oksana V.,Kirillova, Marina V.,Guedes Da Silva, M. Fatima C.,Boca, Roman,Pombeiro, Armando J. L.
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p. 775 - 783
(2014/01/17)
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- Carbon dioxide as a C1 building block for the formation of carboxylic acids by formal catalytic hydrocarboxylation
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A happy marriage of two processes: An effective catalytic system was identified for the direct synthesis of carboxylic acids from non-activated olefins or alcohols, CO2, and H2. Detailed analysis together with labeling studies indicated that the overall hydrocarboxylation of simple olefins results from a combination of the reverse water-gas shift (rWGS) reaction and a hydroxycarbonylation step, each promoted by a rhodium catalyst (see scheme). Copyright
- Ostapowicz, Thomas G.,Schmitz, Marc,Krystof, Monika,Klankermayer, Juergen,Leitner, Walter
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p. 12119 - 12123
(2013/12/04)
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- Tautomeric effect of hydrazone Schiff bases in tetranuclear Cu(ii) complexes: Magnetism and catalytic activity towards mild hydrocarboxylation of alkanes
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Three new tetranuclear copper(ii) complexes [Cu(HL1)] 4·4EtOH (1·4EtOH), [Cu(HL2)]4 (2) and [Cu(H2L3)]4(NO3) 4·2H2O (3·2H2O) have been synthesized using three different hydrazone Schiff base ligands derived from the condensation of the aromatic acid hydrazides 2-hydroxybenzo-, 2-aminobenzo- or benzo-hydrazide, with 2,3-dihydroxybenzaldehyde. Complexes 1 and 3 have been characterized by single crystal X-ray diffraction analysis. The coordinating behaviour of the ligand depends on the nature of the ortho substituent present in the hydrazide moiety. The ligands bearing a strong electron donating group (by resonance) in the ortho position undergo complexation via enolization and deprotonation, whereas the absence of such an effect leads to complexation via the keto form, and two different types of tetranuclear Cu(ii) clusters, viz. open-cubane and cubane, are obtained. Variable temperature magnetic susceptibility measurements of complexes 1 and 3 have been carried out to examine the nature of magnetic interaction between the Cu(ii) centres. All the three complexes (1-3) act as good catalyst precursors towards mild hydrocarboxylation of linear and cyclic alkanes into carboxylic acids in water-acetonitrile medium.
- Sutradhar, Manas,Kirillova, Marina V.,Guedes Da Silva, M. Fatima C.,Liu, Cai-Ming,Pombeiro, Armando J. L.
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p. 16578 - 16587
(2013/12/04)
-
- Topologically unique 2D heterometallic CuII/Mg coordination polymer: Synthesis, structural features, and catalytic use in alkane hydrocarboxylation
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The new two-dimensional (2D) heterometallic CuII/Mg coordination polymer [Cu2Mg2(μ-Htea)2(μ6- pma)(H2O)6]n?6nH2O (1) with an unprecedented [Cu2Mg(μ-O)2(μ-COO)2] - core has been easily generated by aqueous medium self-assembly from copper(II) nitrate, triethanolamine (H3tea), magnesium hydroxide, and pyromellitic acid (H4pma). The crystal structure of 1 is composed of infinite interdigitated 2D metal-organic layers that extend via H-bonds into an intricate 3D supramolecular framework. The topological analysis of 1 discloses a binodal 2,4-connected underlying 2D net with the unique topology described by the point symbol of (64?8?10)(6), further simplification of which leads to an uninodal 4-connected net with the sql topology. Apart from representing a very rare example of the heterometallic Cu/Mg coordination network, compound 1 also acts as an efficient catalyst precursor for the mild single-pot hydrocarboxylation of linear and cyclic C n (n = 5-9) alkanes into the corresponding Cn+1 carboxylic acids.
- Kirillov, Alexander M.,Karabach, Yauhen Y.,Kirillova, Marina V.,Haukka, Matti,Pombeiro, Armando J. L.
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scheme or table
p. 1069 - 1074
(2012/06/18)
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- Fundamental insights into the enantioselectivity of hydrogenations on cinchona-modified platinum and palladium
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The influence of the configuration at the C8 and C9 positions of cinchona alkaloids was investigated by comparing the efficiency of cinchonidine, cinchonine, and 9-epi-cinchonidine as chiral modifiers. In the hydrogenation of ketones (methyl benzoylformate, ketopantolactone, methylglyoxal dimethylacetal, 2,2,2-trifluoroacetophenone) on Pt, a change in the configuration at C9 did not affect the absolute configuration of the main products; however, the ees and rates dropped significantly. In the hydrogenation of α-functionalized olefins (E-2-methyl-2-hexenoic acid, 2-phenylcinnamic acid, and 4-methoxy-6-methyl-2H-pyran-2-one) on Pd, replacement of cinchonidine or cinchonine by epi-cinchonidine diminished the rates and almost eliminated the enantioselection, indicating that a subtle combination of C8 and C9 configurations is required on Pd. DFT calculations of the adsorption of the modifiers and the nonlinear behavior of modifier mixtures revealed that the lower reaction rates observed for 9-epi-cinchonidine-modified surfaces cannot be related to different adsorption strength of this modifier. Additionally, substrate-modifier docking interactions are presented.
- Schmidt, Erik,Bucher, Christoph,Santarossa, Gianluca,Mallat, Tamas,Gilmour, Ryan,Baiker, Alfons
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experimental part
p. 238 - 248
(2012/06/01)
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- New diamondoid-like [Cu3B(μ-O)6] core self-assembled from Bis-Tris biobuffer for mild hydrocarboxylation of alkanes to carboxylic acids
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The new tricopper(ii) complex [Cu3(μ3-BO)(H 3L)3][BF4]·2H2O (1) with an unprecedented diamondoid-like [Cu3B(μ-O)6] core has been easily generated by self-assembly in an aqueous medium from Cu(NO 3)2, NaBF4, NaOH and Bis-Tris (H5L) biobuffer, (HOCH2)3CN(CH2CH2OH) 2. Compound 1 efficiently promotes the mild single-pot hydrocarboxylation, by CO and H2O, of various linear and cyclic Cn (n = 2-8) alkanes into the corresponding Cn+1 carboxylic acids.
- Kirillov, Alexander M.,Karabach, Yauhen Y.,Kirillova, Marina V.,Haukka, Matti,Pombeiro, Armando J. L.
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supporting information; experimental part
p. 6378 - 6381
(2011/08/06)
-
- Mild oxidative functionalization of alkanes and alcohols catalyzed by new mono- and dicopper(II) aminopolyalcoholates
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The new mono- and dicopper(II) complexes [Cu(H3L 1)(NCS)] (1) and [Cu2(μ-HL2) 2(NCS)2] (2) were easily self-assembled from Cu(CH 3COO)2·H2O, NaNCS, NaOH and N,N,N′,N′-tetrakis(2-hydroxyethyl)ethylenediamine (H 4L1) or N-ethyldiethanolamine (H2L 2), respectively. They were fully characterized by IR spectroscopy, ESI-MS(±), elemental and single-crystal X-ray diffraction analyses, and applied as homogeneous catalysts for (i) the oxidation of alkanes by t-BuOOH in air to alkyl peroxides, alcohols and ketones, and in turn the oxidation of alcohols to ketones, and (ii) the single-pot aqueous medium hydrocarboxylation, by CO, H2O and K2S2O8, of various linear and cyclic Cn (n = 5-8) alkanes into the corresponding C n+1 carboxylic acids. Compound 1 was significantly more active in the oxygenation of alkanes and oxidation of alcohols, allowing to achieve 18% yield (TON = 800) of oxygenates in the oxidation of cyclohexane, and 78% yield (TON = 780) of cyclohexanone in the oxidation of cyclohexanol. In alkane hydrocarboxylations, 1 and 2 exhibited comparable activities with the total yields (based on alkane) of carboxylic acids attaining 39%. The selectivity parameters for oxidative transformations were measured and discussed, supporting free-radical mechanisms.
- Kirillov, Alexander M.,Kirillova, Marina V.,Shul'Pina, Lidia S.,Figiel, Pawe? J.,Gruenwald, Katrin R.,Guedes Da Silva, M. Fátima C.,Haukka, Matti,Pombeiro, Armando J.L.,Shul'Pin, Georgiy B.
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experimental part
p. 26 - 34
(2012/01/14)
-
- Mild, single-pot hydrocarboxylation of linear C5-C9 alkanes into branched monocarboxylic C6-C10 acids in copper-catalyzed aqueous systems
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A single-pot method has been developed for the hydrocarboxylation of the liquid C5-C9 alkanes (n-pentane, n-hexane, n-heptane, n-octane, n-nonane and 3-methylhexane) into the branched monocarboxylic C 6-C10 acids bearing one more carbon atom. This method is characterized by a direct, selective and low-temperature (60 °C) hydrocarboxylation reaction of the alkane with carbon monoxide, water (which acts as a reagent besides being a solvent component) and potassium peroxodisulfate, in H2O/MeCN medium. The hydrocarboxylations are markedly enhanced in the presence of a tetracopper(II) triethanolaminate complex as a homogeneous catalyst precursor. Total yields (based on alkane) of carboxylic acids up to 46% (with 97-99% overall selectivity) have been achieved, which are remarkable in the field of alkane functionalization under mild conditions, especially for a C-C bond formation reaction in aqueous acid-solvent-free medium. The regio- and bond selectivity parameters have been determined and a free radical mechanism has been proposed.
- Kirillova, Marina V.,Kirillov, Alexander M.,Pombeiro, Armando J.L.
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experimental part
p. 106 - 113
(2012/04/04)
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- Alkanes to carboxylic acids in aqueous medium: Metal-free and metal-promoted highly efficient and mild conversions
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A convenient and clean route to transform, in aqueous medium, various alkanes to carboxylic acids via single-pot carboxylation with CO and water, under mild conditions, has been achieved, proceeding efficiently and selectively even without any metal catalyst and any acid additive, at low temperatures; the relevant hydroxylating role of H2O and radical mechanisms are disclosed by radical-trap, H218O and DFT studies. The Royal Society of Chemistry 2009.
- Kirillova, Marina V.,Kirillov, Alexander M.,Kuznetsov, Maxim L.,Silva, Jose A. L.,Frausto Da Silva, Joao J. R.,Pombeiro, Armando J. L.
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supporting information; experimental part
p. 2353 - 2355
(2009/09/06)
-
- Hydrocarboxylation of terminal alkenes in supercritical carbon dioxide
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The catalytic hydrocarboxylation of linear alkenes to carboxylic acids using supercritical carbon dioxide as a solvent was studied. High selectivities in acids have been obtained. The best results were achieved when adding a perfluorinated surfactant to the reaction mixture (93% conversions and ca. 80% selectivity). Comparative multinuclear high-pressure NMR spectroscopic studies in [D8]THF and in supercritical CO2 show the formation of Pd0 species. Wiley-VCH Verlag GmbH & Co. KGaA, 2008.
- Estorach, Clara Tortosa,Orejon, Arantxa,Ruiz, Nuria,Masdeu-Bulto, Anna M.,Laurenczy, Gabor
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experimental part
p. 3524 - 3531
(2009/02/07)
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- METHOD FOR THE CONVERSION, UNDER MILD CONDITIONS AND IN AQUEOUS MEDIUM, OF GASEOUS AND LIQUID ALKANES INTO CARBOXYLIC ACIDS
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The present invention concerns a new efficient method for the selective transformation, under mild conditions and in aqueous medium, of gaseous (ethane, propane and n-butane) and liquid (n-pentane, n-hexane, cyclopentane and cyclohexane) alkanes into carboxylic acids bearing one more carbon atom, characterized by a single-pot low- temperature (25-60 °C) reaction of the alkane with carbon monoxide in water/acetonitrile liquid medium, either in the absence or in the presence of a metal catalyst, in systems containing also an oxidant (a peroxodisulphate salt).
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Page/Page column 7-13
(2008/12/07)
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- IBX-mediated oxidation of primary alcohols and aldehydes to form carboxylic acids
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Under mild conditions and without the use of toxic metals, the oxidation of primary alcohols and aldehydes to the corresponding carboxylic acids with 1-hydroxy-1,2-benziodoxole-3(1H)-one-1-oxide (IBX) proceeds in the presence of 1-hydroxypyridine or N-hydroxysuccinimide (see scheme). The reaction tolerates a wide variety of functional groups.
- Mazitschek, Ralph,Muelbaier, Marcel,Giannis, Athanassios
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p. 4059 - 4061
(2007/10/03)
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- Syntheses of female sex pheromone precursors of pine sawfly species and of some structurally related methyl-branched long-chain 2-alkanols.
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3,7-Dimethyl-2-undecanol, 3,7,9-trimethyl-2-tridecanol, and 3,7, 11-trimethyl-2-tridecanol were synthesized as racemic mixtures in moderate yields. The alcohols are known precursors of the female sex pheromones of the pine sawfly species Diprion nipponica, Macrodiprion nemoralis, and Microdiprion pallipes, respectively. Stereoisomeric mixtures of 3,8,12-trimethyl-2-tridecanol, erythro-(2R,3R, 11R/S)-3,11-dimethyl-2-tetradecanol, 3,5-dimethyl-2-tetradecanol, and 5,7-dimethyl-2-tetradecanol, structurally related to sex pheromone alcohol precursors of pine sawfly species, were also synthesized in moderate yields. The key reaction in the syntheses was the ring opening of gamma-butyrolactones by using different alkyl lithiums as nucleophiles.
- Hedenstroem, Erik,Andersson, Fredrik
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p. 1237 - 1254
(2007/10/03)
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- Stereoselective reactions of acyclic allylic phosphates with organocopper reagents
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A series of acyclic allylic alcohols of general structure R1CH=CHCH(OH)R2 were resolved by Sharpless kinetic resolution. The hydroxyl groups of these enantiomerically enriched alcohols were derivatized to diethyl phosphates, and the derivatives were reacted with organocopper reagents. Cleanest substitution reactions were observed with reagents R32CuCNLi2. With R1 = Me and R3 = n-Bu, the size of R2 affected both the regioselectivity and stereoselectivity of the displacement. Larger R2 groups gave higher regio- and stereoselectivities: with R2 = 3-pentyl, >98% SN2′ regioselectivity and > 98% anti stereoselectivity were observed. Bn2CuCNLi2 gave stereoselectivities comparable to those observed with n-Bu2CuCNLi2 but t-Bu2CuCNLi2 exhibited much lower diastereofacial preference.
- Belelie,Chong
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p. 5552 - 5555
(2007/10/03)
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- Novel palladium(II) complex containing a chelating anionic N-O ligand: Efficient carbonylation catalyst
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(matrix presented) A novel palladium(II) complex containing chelating anionic pyridine-2-carboxylato and labile tosylato ligands is a highly efficient catalyst for the carbonylation of organic alcohols and olefins to carboxylic acids/esters. Carbonylation of primary, secondary, and tertiary alcohols as well as linear and functionalized terminal olefins was studied. In all cases remarkable activity and selectivity were observed. The catalyst is stable under reaction conditions even in the absence of excess phosphine ligands.
- Jayasree,Seayad,Chaudhari
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p. 203 - 206
(2007/10/03)
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- Synthesis of compounds with predetermined chirality
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A method for synthesizing enantiomerically enriched chemical intermediates with predetermined chirality is described. The method comprises formation of a pseudoephedrine amide, followed by stereoselective alkylation at the alpha carbon. The chiral auxiliary can then be cleaved off, affording chiral end products useful for further transformations. The enantiomeric enrichment of the chiral end products may exceed 98%, and the chiral auxiliary can be recovered. Novel amides of pseudoephedrine used in this method are also disclosed.
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- Ruthenium-BINAP asymmetric hydrogenation catalyst
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A ruthenium-phosphine complex represented by the formula: wherein n is an integer of from 1 to about 10; and X and Y independently represent nonchelating anionic ligands.
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- Antiparasitic agents
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The invention provides novel compounds having the formula: STR1 wherein R when taken individually is H; R1 when taken individually is H or OH; R and R1 when taken together represent a double bond; R2 is an alpha-branched C3 -C8 alkyl, alkenyl, alkynyl, alkoxyalkyl or alkylthioalkyl group; a C3 -C8 cycloalkyl, C5 -C8 cycloalkenyl or C5 -C8 cycloalkylalkyl group, any of which may be substituted by methylene or one or more C1 -C4 alkyl groups or halo atoms; or a 3 to 6 membered oxygen or sulphur containing heterocyclic ring which may be substituted by one or more C1 -C4 alkyl groups or halo atoms; R3 is hydrogen or methyl; R4 is H or 4'-(alpha-L-oleandrosyl)-alpha-L-oleandrosyloxy with the proviso that when R2 is alkyl it is not isopropyl or sec-butyl; when R4 is H, each of R and R1 is H, and R2 is not methyl or ethyl; and when R4 is H, R is H, R1 is OH, and R2 is not 2-buten-2-yl, 2-penten-2-yl or 4-methyl-2-penten-2-yl. The compounds are broad spectrum antiparasitic agents having utility as anthelmintics, ectoparasiticides, insecticides and acaricides. The invention also provides a process for producing the novel avermectin and milbemycin derivatives by adding a carboxylic acid or derivative thereof to a fermentation of an avermectin or milbemycin producing organism.
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