5032-65-5Relevant academic research and scientific papers
Rhodium Complexes in P-C Bond Formation: Key Role of a Hydrido Ligand
Varela-Izquierdo, Víctor,Geer, Ana M.,Navarro, Janeth,López, José A.,Ciriano, Miguel A.,Tejel, Cristina
supporting information, p. 349 - 358 (2021/01/13)
Olefin hydrophosphanation is an attractive route for the atom-economical synthesis of functionalized phosphanes. This reaction involves the formation of P-C and H-C bonds. Thus, complexes that contain both hydrido and phosphanido functionalities are of gr
Hydrophosphination of Activated Alkenes by a Cobalt(I) Pincer Complex
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)
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.).
A bench-stable copper photocatalyst for the rapid hydrophosphination of activated and unactivated alkenes
Dannenberg, Steven G.,Waterman, Rory
supporting information, p. 14219 - 14222 (2020/11/24)
Cu(acac)2 (1) is a highly active catalyst for the hydrophosphination of alkenes. Photocatalytic conditions are critical, and provide high conversions with unactivated substrates that have never before been reported with an air-stable catalyst or at ambient temperature. The commercial availability, ease of use, and broad substrate scope of compound 1 make hydrophosphination more available to synthetic chemists.
Photocatalytic Hydrophosphination of Alkenes and Alkynes Using Diphenylphosphine and Triamidoamine-Supported Zirconium
Novas, Bryan T.,Bange, Christine A.,Waterman, Rory
supporting information, p. 1640 - 1643 (2019/01/04)
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.
Palladium nanocatalysts in glycerol: Tuning the reactivity by effect of the stabilizer
Reina, Antonio,Serrano-Maldonado, Alejandro,Teuma, Emmanuelle,Martin, Erika,Gómez, Montserrat
, p. 22 - 27 (2017/10/24)
Palladium nanoparticles (PdNPs) prepared in neat glycerol containing TPPTS (tris(3-sulfophenyl)phosphine trisodium salt) or cinchona-based alkaloids (cinchonidine, quinidine) as capping agents, were applied as catalysts in fluoride-free Hiyama couplings and conjugate additions with the aim of evaluating the influence of the stabilizer in the catalytic reactivity. Therefore, PdNPs stabilized by phosphine favored C–C cross-couplings, whereas those containing alkaloids showed enhanced suitability for C–C homo-couplings and conjugate additions. The metal/stabilizer coordination mode, i.e. Pd–P dative bond and π-π interaction between quinoline moiety and palladium surface, is certainly key for the stabilization of different active metallic species and then promoting distinctive catalytic pathways.
Visible Light Photocatalysis Using a Commercially Available Iron Compound
Pagano, Justin K.,Bange, Christine A.,Farmiloe, Sarah E.,Waterman, Rory
supporting information, p. 3891 - 3895 (2017/10/30)
[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.
Tin-catalyzed hydrophosphination of alkenes
Stelmach, John P. W.,Bange, Christine A.,Waterman, Rory
, p. 6204 - 6209 (2016/04/26)
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.
Catalyst- and solvent-free hydrophosphination and multicomponent hydrothiophosphination of alkenes and alkynes
Moglie, Yanina,González-Soria, María José,Martín-García, Iris,Radivoy, Gabriel,Alonso, Francisco
supporting information, p. 4896 - 4907 (2016/10/06)
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.
Cobalt Phosphino-α-Iminopyridine-Catalyzed Hydrofunctionalization of Alkenes: Catalyst Development and Mechanistic Analysis
Chu, Wan-Yi,Gilbert-Wilson, Ryan,Rauchfuss, Thomas B.,Van Gastel, Maurice,Neese, Frank
supporting information, p. 2900 - 2914 (2016/11/02)
A family of CoCl2(PNpy) complexes were prepared, where PNpy = 2-iminopyridyl-phosphine ligands derived from aminoalkyl and aminoaryl phosphines and 2-keto- and 2-formylpyridines. Reduction of CoCl2(PNpy) complexes in the presence of
Inner- and Outer-Sphere Roles of Ruthenium Phosphido Complexes in the Hydrophosphination of Alkenes
Belli, Roman G.,Burton, Krista M. E.,Rufh, Stephanie A.,McDonald, Robert,Rosenberg, Lisa
, p. 5637 - 5646 (2015/12/23)
An inner-sphere synthetic cycle for the hydrophosphination of alkenes is proposed, based on observed [2 + 2] cycloaddition of a wide range of alkenes at a coordinatively unsaturated Ru=PR2 complex. Key intermediates in the cycle were prepared, and their reactions with various organic acid/base pairs were examined to identify both new ruthenium precursors and base cocatalysts that allow turnover of the proposed cycle. Two new cationic ruthenium indenyl phosphine complexes were isolated and structurally characterized. Although preliminary screening studies show the moderate activity of these and related neutral phosphido complexes for catalytic hydrophosphination of acrylonitrile by both HPPh2 and HPCy2, and comparable activity for the hydrophosphination of tert-butyl acrylate by HPPh2, no activity was observed for the analogous hydrophosphination of 1-hexene. This is attributed to strong binding of the substrate phosphine to the unsaturated, planar Ru - PR2 fragment generated in situ, which inhibits the inner-sphere, alkene cycloaddition mechanism. An alternative, outer-sphere Michael addition process, involving a saturated complex with a strongly nucleophilic pyramidal Ru-PR2 ligand, is proposed to rationalize the observed selectivity for catalytic hydrophosphination of activated, but not simple, alkenes. Implications for further catalyst development are discussed.
