- Valorization of furfural using ruthenium (II) complexes containing phosphorus-nitrogen ligands under homogeneous transfer hydrogen condition
-
In this paper, we report the catalytic activity of a series of ruthenium (II) complexes containing phosphorus-nitrogen bidentated (P-N) ligands in the hydrogenation of furfural via hydrogen transfer reaction using two hydrogen donor sources: 2-propanol in basic medium and formic acid under mild conditions. The results showed that all the ruthenium complexes studied are catalytically active in the hydrogenation of furfural by hydrogen transfer reaction; they showed 100% conversion with both hydrogen sources. However, selectivities towards the formation of furfuryl alcohol were better when formic acid was used. It was also found that the reaction studied in a basic medium competes with the Cannizzaro reaction, obtaining furfuryl alcohol and furoic acid in a 70/30 ratio; on the other hand, using formic acid as the hydrogen source yields furfuryl alcohol with 100% selectivity. Although formic acid can be used as a hydrogen source successfully. The optimal substrate/acid ratio was found to be 1:1, as a higher concentration of formic acid can cause catalyst decomposition. The yielded products, furfuryl alcohol and furoic acid, obtained from renewable sources, have multiple applications in the organic chemical industry, replacing or complementing similar fossil-derived products.
- Aguirre, Pedro,Aranda, Braulio,López, Vicente,Moya, Sergio A.,Parra-Melipán, Sebastián,Valdebenito, Gonzalo
-
-
Read Online
- Photocatalytic Hydrophosphination of Alkenes and Alkynes Using Diphenylphosphine and Triamidoamine-Supported Zirconium
-
Reactions of alkene or alkyne with diphenylphosphine and catalytic [κ5-N,N,N,N,C-(Me3SiNCH2CH2)2NCH2CH2NSiMe2CH2]Zr (1) are greatly enhanced under photolysis, providing viable catalytic hydrophosphination with a broad substrate scope. Whereas diphenylphosphine had been an inaccessible substrate under thermal conditions, complete conversion of alkene substrates to tertiary phosphine is achieved in as little as four hours at ambient temperature with 1 under ultraviolet irradiation. Previously inactive alkenes are now hydrophosphination substrates with diphenylphosphine to produce tertiary phosphine ligands possessing tunable steric and electronic properties.
- Novas, Bryan T.,Bange, Christine A.,Waterman, Rory
-
-
Read Online
- Catalytic hydrophosphination of styrenes
-
(equation presented) The first example of intermolecular hydrophosphination of styrenes catalyzed by Ni and Pd complexes is described. The reaction of Ph2PH with styrene, 4-vinylpyridine, 2-vinylpyridine, 4-methoxystyrene, 2-methoxystyrene, and 5-vinyl-2-methylpyridine in benzene under Ni[P(OEt)3]4 catalysis proceeds with high yield and selectivity to give only anti-Markovnikov product.
- Shulyupin, Mstislav O.,Kazankova, Marina A.,Beletskaya, Irina P.
-
-
Read Online
- t-BuOK-catalyzed addition phosphines to functionalized alkenes: A convenient synthesis of polyfunctional phosphine derivatives
-
The use of t-BuOK in DMSO allows a smooth addition of Ph2PH, Cy2PH and Ph2P(O)H to various functionalized alkenes leading to polyfunctional phosphines in good yields. This method has been used to prepare precursors for P,P- and P,N-ligands.
- Bunlaksananusorn, Tanasri,Knochel, Paul
-
-
Read Online
- A Functionalized Alkyldiphenylphosphine as an Efficient and Mild Reagent in CCl4-Promoted Substitution Reactions: Kinetics and Mechanism of the Reaction in CHCl3
-
(Pyrid-2-ylethyl)diphenylphosphine can be used at 35-45 deg C in carbon tetrachloride-chloroform to give high yields of primary and secondary alkyl chlorides from the corresponding alcohols. The isolation of products is simplified by removal of the phosphorus-containing products by extraction into a dilute aqueous acid solution.The complex reaction was studied by 31P NMR.The rate constants based on the decay of phosphine are reported.The rapid conversion of alcohols proceeds equally via chlorination by CCl3 (path A) and by Cl (path B).The rates of formation and decay of an isobutoxyphosphonium intermediate, Cl, have been measured with 31P NMR.
- Toto, Susan D.,Doi, Joyce Takahashi
-
-
Read Online
- Visible Light Photocatalysis Using a Commercially Available Iron Compound
-
[CpFe(CO)2]2 (1) (Cp = η5-C5H5) is an effective precatalyst for the hydrophosphination of alkenes with Ph2PH under visible light irradiation, which appears to be a unique way to promote metal-catalyzed hydrophosphination. Additionally, 1 is a photocatalyst for the dehydrogenation of amine boranes and formation of siloxanes from tertiary silanes. These reactions have similar, if not improved, reactivity over the same transformations using 1 or related CpFeMe(CO)2 under UV irradiation, consistent with the notion that hydrophosphination with 1 proceeds via formation of CpFe(CO)2?. These results demonstrate that catalyst selection can avail the use of commercially available LED bulbs as photon sources, potentially replacing mercury arc lamps or other energy intensive processes in known or new catalytic reactions.
- Pagano, Justin K.,Bange, Christine A.,Farmiloe, Sarah E.,Waterman, Rory
-
-
Read Online
- Hydrophosphination of Activated Alkenes by a Cobalt(I) Pincer Complex
-
Herein we report the synthesis of three heteroleptic first-row transition metal(II) complexes containing carbazolido NNN pincer ligands and conversion to the corresponding metal(I)-carbonyl complexes via a reductive carbonylation route. These complexes are precatalysts for the hydrophosphination of activated alkenes, affording a cobalt-catalysed hydrophosphination process that solely and selectively yields the β addition (anti-Markovnikov) product. The scope of this transformation has been investigated using a variety of activated alkenes. Isolation and characterisation of substrate-coordinated intermediates reveal available coordination sites, which provide insight into the proposed catalytic cycle. (Figure presented.).
- Nolla-Saltiel, Roberto,Geer, Ana M.,Taylor, Laurence J.,Churchill, Olivia,Davies, E. Stephen,Lewis, William,Blake, Alexander J.,Kays, Deborah L.
-
supporting information
p. 3148 - 3157
(2020/06/08)
-
- Neutral and Cationic Zirconium Complexes Bearing Multidentate Aminophenolato Ligands for Hydrophosphination Reactions of Alkenes and Heterocumulenes
-
Zirconium complexes supported by multidentate aminophenolato ligands were synthesized and characterized. The catalytic activities of neutral zirconium complexes and their cationic derivatives in the hydrophosphination of alkenes as well as heterocumulenes have been investigated and compared. Neutral complex 1 bearing a multidentate amino mono(phenolato) ligand exhibited high activity in hydrophosphination of simple alkenes, and anti-Markovnikov products were obtained in 37-94% yields at room temperature. Cationic species generated in situ from complex 3 stabilized by a bis(phenolato) ligand were found to be more active for hydrophosphination of heterocumulenes, i.e., carbodiimides and isocyanates, and gave phosphaguanidines and phosphaureas in 67-93% yields. The Lewis acidity and coordination space of metal centers are modified through changes in the ligand structure, which is found to significantly influence catalytic activity. These complexes are among the most active group 4 metal-based catalysts for hydrophosphination reactions.
- Zhang, Yu,Qu, Liye,Wang, Yaorong,Yuan, Dan,Yao, Yingming,Shen, Qi
-
p. 139 - 149
(2018/01/11)
-
- Iron catalysis for the synthesis of ligands: Exploring the products of hydrophosphination as ligands in cross-coupling
-
Catalytic hydrophosphination is a useful technique for the synthesis of phosphines, however, the phosphine products have been little exploited as ligands in catalysis. We have selected three phosphines prepared by iron catalyzed hydrophosphination and used them as ligands in a series of cross-coupling reactions: Heck, Suzuki-Miyaura and Buchwald-Hartwig. Rather than limit the chemistry to simple cross-coupling partners which are almost guaranteed to perform well in these transformations, industrially relevant substrates which are challenging from and electronic and/or steric perspective, along with substrates which contain several heteroatoms, were explored in order to gauge the true potential of these phosphine ligands.
- Espinal-Viguri, Maialen,Mahon, Mary F.,Tyler, Simon N.G.,Webster, Ruth L.
-
-
- Catalyst- and solvent-free hydrophosphination and multicomponent hydrothiophosphination of alkenes and alkynes
-
The hydrophosphination of carbon-carbon multiple bonds has been generally performed under acid, base or metal catalysis in different solvents. Herein, alkyl and alkenyl tertiary phosphines are obtained by the addition of diphenylphosphine to alkenes and alkynes, respectively, in the absence of a solvent and a catalyst. In the presence of elemental sulfur, the corresponding alkyl and alkenyl tertiary phosphine sulfides are synthesized in a three-component process. These simple methods, which meet most of the principles of Green Chemistry, are highly regioselective towards the anti-Markovnikov products and diastereoselective towards the Z alkenyl phosphines. The mechanistic aspects of the reactions are also tackled and the efficiency of the latter is compared with that of the catalytic methods.
- Moglie, Yanina,González-Soria, María José,Martín-García, Iris,Radivoy, Gabriel,Alonso, Francisco
-
supporting information
p. 4896 - 4907
(2016/10/06)
-
- Synthesis and molecular structures of divalent bridged bis(guanidinate) europium complexes and their application in intermolecular hydrophosphination of alkenes and alkynes
-
The reaction of anhydrous EuCl3 with one equiv. of lithium salt of a three-carbon bridged bis(guanidinate) Li2L1 (L1 = [iPr(Me3Si)NC(NiPr)N(CH2)3NC(NiPr)N(SiMe3)iPr]) in THF afforded chloride EuIIIL1Cl(THF)2 (1). The reduction reaction of complex 1 with Na/K alloy in a molar ratio of 1?:?1.2 in THF gave a novel EuII complex supported by an unexpected new bridged bis(guanidinate) ligand L3, [EuIIL3]2 (L3 = [iPr(Me3Si)NC(NiPr)N(CH2)3N(SiMe3)C(NiPr)2]) (2), through the redistribution of one guanidinate in L1 during the reduction. Complex 2 was structurally characterized to be a binuclear complex in which two Eu metals are connected together by two L3 ligands that adopted a μ-η1:η2:η2 coordination mode for one L3 ligand and a μ-η2:η2:η2 mode for the other. Treatment of the in situ formed EuIIIL2Cl(THF)2 (L2 = 1,8-C10H6{NC(NiPr)(NHiPr)}2) by the reaction of EuCl3 with 0.5 equiv. of [Li2L22Li2] in THF with Na/K alloy yielded a novel EuII complex [EuIIL2(THF)]2 (3) in good yield. Complex 3 was characterized by an X-ray crystal structure analysis. Complex 3 features an unusual μ-η1:η2:η2 coordination mode of the bridged bis(guanidinate) ligand onto EuII. Complexes 2 and 3 are efficient pre-catalysts for the intermolecular hydrophosphination of alkenes and alkynes to give exclusively anti-Markovnikov products and mainly anti-addition products for the alkyne reactions. For these transformations, the best performances were observed with complex 2.
- Liu, Qianqian,Wang, Chuanyong,Zhang, Xingmin,Xue, Mingqiang,Yao, Yingming,Zhang, Yong,Shen, Qi
-
supporting information
p. 10447 - 10454
(2016/12/06)
-
- A Study of Two Highly Active, Air-Stable Iron(III)-μ-Oxo Precatalysts: Synthetic Scope of Hydrophosphination using Phenyl- and Diphenylphosphine
-
The importance of phosphines in synthetic chemistry cannot be underestimated. Catalytic hydrophosphination offers an ideal method to prepare P?C bonds without the need for harsh reaction conditions or stoichiometric amounts of waste by-product. We herein report our studies into two biocompatible iron(III) complexes in hydrophosphination chemistry using diphenylphosphine under mild and benign reaction conditions (room temperature, solvent-free) and our extended exploration of hydrophosphination with phenylphosphine, which can be tuned to operate in the absence of catalyst under thermal conditions for single hydrophosphination or solvent-free with an iron(III) precatalyst to generate the products of double hydrophosphination. (Figure presented.).
- Gallagher, Kimberley J.,Espinal-Viguri, Maialen,Mahon, Mary F.,Webster, Ruth L.
-
p. 2460 - 2468
(2016/08/16)
-
- N-Heterocyclic Carbene-Ytterbium Amide as a Recyclable Homogeneous Precatalyst for Hydrophosphination of Alkenes and Alkynes
-
The N-heterocyclic carbene-ytterbium(II) amides (NHC)2Yb[N(SiMe3)2]2 (1: NHC: 1,3,4,5-tetramethylimidazo-2-ylidene (IMe4); 2: NHC: 1,3-diisopropyl-4,5-dimethylimidazol-2-ylidene (IiPr)) and the NHC-stabilized rare-earth phosphide (IMe4)3Yb(PPh2)2 (3) have been synthesized and fully characterized. Complexes 1-3 are active precatalysts for the hydrophosphination of alkenes, alkynes, and dienes and exhibited much superior catalytic activity to that of the NHC-free amide (THF)2Yb[N(SiMe)2]2. Complex 1 is the most active precursor among the three complexes. In particular, complex 1 can be recycled and recovered from the reaction media after the catalytic reactions. Furthermore, it was found that complex 3 could catalyze the polymerization of styrene to yield atactic polystyrenes with low molecular weights. To the best of our knowledge, complex 1 represents the first rare-earth complex that can be recovered after catalytic reactions.
- Yuan, Jia,Hu, Hongfan,Cui, Chunming
-
p. 5778 - 5785
(2016/04/20)
-
- Tin-catalyzed hydrophosphination of alkenes
-
Simple tin derivatives, Cp?2SnCl2 (1) and Ph2SnCl2 (2), catalyze the hydrophosphination of alkene substrates with diphenylphosphine. Competitive dehydrocoupling to give Ph4P2 was observed, but this side reaction can be mitigated when the catalysis is conducted under an H2 atmosphere. Efforts to prepare stable tin bis(phosphido) compounds commonly resulted in decomposition to Ph4P2. Lewis acidic inorganic tin compounds do not show dehydrocoupling reactivity. It was found that the Lewis acid, B(C6F5)3, is able to engage in the hydrophosphination of alkenes, but it is poorly effective under the conditions tested.
- Stelmach, John P. W.,Bange, Christine A.,Waterman, Rory
-
p. 6204 - 6209
(2016/04/26)
-
- Room temperature hydrophosphination using a simple iron salen pre-catalyst
-
Phosphines are fundamentally important to the fine chemicals, pharmaceutical and agrochemical industries. Reported is the first example of alkene hydrophosphination using a designed iron pre-catalyst which yields the anti-Markovnikov products in high yield at room temperature. The phosphine products are excellent pro-ligands for Fe-catalyzed Negishi cross-coupling. This journal is
- Gallagher,Webster
-
supporting information
p. 12109 - 12111
(2015/01/08)
-
- Solvent- and catalyst-free regioselective hydrophosphanation of alkenes
-
The hydrophosphanation of alkenes, an atom-economy process typically promoted by radicals or metal species, has been shown to take place in the absence of a catalyst, under solvent-free conditions and in a regioselective manner.
- Alonso, Francisco,Moglie, Yanina,Radivoy, Gabriel,Yus, Miguel
-
supporting information
p. 2699 - 2702
(2012/11/07)
-
- Fluoride-mediated phosphination of alkenes and alkynes by silylphosphines
-
Regioselective phosphination of carbon-carbon unsaturated bonds by a fluoride-mediated reaction of silylphosphines is described. Alkenes and alkynes having a directing group, such as an aromatic or a carbonyl group, reacted to form a carbon-phosphorus bon
- Hayashi, Minoru,Matsuura, Yutaka,Watanabe, Yutaka
-
p. 9167 - 9169
(2007/10/03)
-
- Synthesis of alkyl(diphenyl)phosphines by hydrophosphination of vinylarenes catalyzed by transition metal complexes
-
Hydrophosphination of styrenes and their heteroanalogs with diphenylphosphine in the presence of nickel or palladium complexes was accomplished for the first time. The reaction ensures high yields and regioselectivity: the corresponding anti-Markownikoff adducts are exclusively formed.
- Kazankova,Shulyupin,Borisenko,Beletskaya
-
p. 1479 - 1484
(2007/10/03)
-
- Process for the preparation of a butene
-
Process for the preparation of 1-butene by dimerization of ethylene in the presence of an aprotic solvent and a catalytic system prepared by combining (a) a Pd compound, (b) an anion of an acid having a pKa = 1 N atoms which atoms bear no H atoms and in which compound each N atom is connected to the P atom by an organic bridging group containing >= 1 C atom in the bridge.
- -
-
-
