Novel functionalised P-ligands: advances and application

Odinets, Irina L.; Vinogradova, Natalya M.; Matveeva, Ekaterina V.; Golovanov, Denis D.; Keglevich, György; Kollár, László; Roeschenthaler, G.-V.; Mastryukova, T. A.

doi:10.1016/j.jorganchem.2004.09.030

Cited by 17 publications

(13 citation statements)

References 23 publications

(31 reference statements)

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“…There are numerous silane reducing agents for the preparation of phosphanes from phosphanones in the literature, but in most of those cases it is difficult to get the product from the reaction mixture, or to avoid using a solvent, such as benzene. 24,28,29 We tried to find an easy and simple way for the deoxygenation of phosphanones. First triphenylphosphanone (17) was used as a model compound to investigate the reduction.…”

Section: Resultsmentioning

confidence: 99%

“…There are reported reductions using triethoxysilane, but in all cases Ti compounds and a solvent, for example benzene are used. [24][25][26][27][28][29][30] In this paper we report an easy way to deoxygenate phosphanones using trimethoxy-or triethoxysilanes without a solvent and a catalyst, gaining macrocycles 1, (R,R)-2, (S,S)-3, (S,S)-4 containing a triphenylphosphane unit. Crown ethers 1 and 5 are already known compounds 14 , here we describe a new route for their preparation, which gives better yields.…”

Section: Introductionmentioning

confidence: 99%

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Synthesis of achiral and new chiral crown ethers containing a triphenylphosphane unit

Szabó¹,

Petri²,

Gergely³

et al. 2015

Arkivoc

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Synthesis and characterization of achiral 1 and new chiral macrocycles (R,R)-2, (S,S)-3 and (S,S)-4 containing a triphenylphosphanone unit have been accomplished. A new method was used for the reduction of phosphanones to phosphanes. Using this method new potential catalyst ligands 15, (R,R)-16, (S,S)-17 and (S,S)-18 containing a triphenylphosphane unit were synthesized and characterized. These ligands are promising candidates for coordination chemistry studies and homogeneous catalytic reactions.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Synthesis of achiral and new chiral crown ethers containing a triphenylphosphane unit

Szabó¹,

Petri²,

Gergely³

et al. 2015

Arkivoc

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“…Therefore we applied a reduction protocol to phosphane oxide 6 using trichlorosilane and triethylamine, which is known to lead to inversion of the configuration at the phosphorus. [13][14][15] Complete conversion was verified by 31 P NMR spectroscopy. The 31 P NMR peak of starting phosphane oxide 6 at δ = 28.5 ppm had disappeared completely in favour of a peak at -7.3 ppm, corresponding to the phosphane.…”

Section: Resultsmentioning

confidence: 99%

“…We tentatively attribute this fact to a rapid homeomorphic isomerisation in solution, [19] which is made possible by the long and flexible arms of the macrobicyclic cage. The derivative phosphane-borane complex 7 was synthesised from phosphane oxide 6 via reduction with tri- chlorosilane proceeding with retention of the configuration at the phosphorus, [12][13][14] and subsequent quenching with borane-tetrahydrofuran complex (Scheme 3). [13] Scheme 3.…”

Section: Resultsmentioning

confidence: 99%

“…The derivative phosphane-borane complex 7 was synthesised from phosphane oxide 6 via reduction with tri- chlorosilane proceeding with retention of the configuration at the phosphorus, [12][13][14] and subsequent quenching with borane-tetrahydrofuran complex (Scheme 3). [13] Scheme 3. Isomerisation experiment of 6 (left) and synthesis of phosphane-borane complex 7 (right).…”

Section: Resultsmentioning

confidence: 99%

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Synthesis, Derivatisation and Structural Characterisation of a New Macrobicyclic Phosphane Oxide Cryptand

2008

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Carbonylation of Alkenes and Dienes

Kégl

2008

Modern Carbonylation Methods

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In the beginning, only cobalt catalysts were utilized for hydroformylation under relatively vigorous conditions. The moderate selectivity of the generally more desired linear isomers, the substantial formation of by-products, and the low stability of the catalysts forced more appropriate catalytic systems to be developed. Using donor ligands such as phosphanes resulted in an increase in the linear selectivity. Rhodium-containing catalysts, however, permitted the use of much milder conditions in combination with suitable ligands. Other transition metals such as ruthenium, palladium, platinum, and iridium also tended to show activity for hydroformylation, albeit a vast majority of works on hydroformylation still concentrated on rhodium-containing systems. Cobalt CatalystsThe initial rate of Co 2 (CO) 8 -catalyzed cyclohexene hydroformylation, triethyl orthoformate carbonylation, and CoH(CO) 4 formation from Co 2 (CO) 8 and H 2 is reduced by the addition of dinitrogen, argon, or xenon. It is assumed that the additional gas competes with one or more reactants for a coordinatively unsaturated site responsible for their activation, thus affecting the reaction rate [1].The carbonylation reaction of propylene oxide in the presence of various [Lewis acid] þ [Co(CO) 4 ] À salts was investigated using in situ attenuated total reflection infrared (ATR-IR) spectroscopy. b-Alkoxy-acyl-cobalttetracarbonyl species were found to be key intermediates from which two reaction routes start depending on the applied Lewis acid. Labile Lewis acid-alkoxy combinations primarily favor the production of lactone products [2].The reaction of olefins (1-octene, 3,3-dimethylbutene, cyclohexene) introduced into a preequilibrated Co 2 (CO) 8 þ H 2 system was investigated by high-pressure infrared spectroscopy. Based on the observed induction period for the formation of the corresponding aldehyde, the decrease in HCo(CO) 4 concentration and increase in Co 2 (CO) 8 concentration during the induction period, the active catalytic species of the type H x Co y (CO) z was proposed [3]. Experiments with isotope mixtures of H 2 /D 2 in the gas phase during the various steps of the reaction showed that the ratio of H/D isotopes in the hydrocarbon portion of the aldehyde product correlates with the HCo(CO) 4 /DCo(CO) 4 ratio in solution, whereas the RC(¼O)H/RC(¼O)D product ratio correlates with the H 2 /D 2 in the gas phase. It was concluded that the dominant pathway for the hydrogenolysis step in this type of hydroformylation is the direct reaction of hydrogen or deuterium with the acyl complex intermediate [4].The effect of argon (280 bar) on the rate of aldehyde formation in 1-hexene hydroformylation catalyzed by Co 2 (CO) 8 at 50 C, 70 bar P(CO) and 85 bar P(H 2 ) in toluene was investigated by high-pressure FT-IR spectroscopy. The initial rate of the reaction was found to be reduced by the presence of argon. A similar effect was observed in the RhH(CO)(PPh 3 ) 3 -catalyzed cyclohexene hydroformylation reaction [5]. 162j 7 Carbonylation of Alkenes and D...

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Novel functionalised P-ligands: advances and application

Cited by 17 publications

References 23 publications

Synthesis of achiral and new chiral crown ethers containing a triphenylphosphane unit

Synthesis of achiral and new chiral crown ethers containing a triphenylphosphane unit

Synthesis, Derivatisation and Structural Characterisation of a New Macrobicyclic Phosphane Oxide Cryptand

Carbonylation of Alkenes and Dienes

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