1024-34-6Relevant articles and documents
Decarbonylative Phosphorylation of Carboxylic Acids via Redox-Neutral Palladium Catalysis
Liu, Chengwei,Ji, Chong-Lei,Zhou, Tongliang,Hong, Xin,Szostak, Michal
, p. 9256 - 9261 (2019)
We describe the direct synthesis of organophosphorus compounds from ubiquitous aryl and vinyl carboxylic acids via decarbonylative palladium catalysis. The catalytic system shows excellent scope and tolerates a wide range of functional groups (>50 examples). The utility of this powerful methodology is highlighted in the late-stage derivatization directly exploiting the presence of the prevalent carboxylic acid functional group. DFT studies provided insight into the origin of high bond activation selectivity and P(O)-H isomerization pathway.
Cu(I) complexes with diethoxyphosphoryl-1,10-phenanthrolines in catalysis of C-C and C-heteroatom bonds formation
Mitrofanov, A.Yu.,Bessmertnykh-Lemeune,Beletskaya
, p. 297 - 301 (2015)
Diethoxyphosphoryl substituted 1,10-phenanthroline copper(I) complexes were tested as catalysts in the Sonogashira-type reaction, α-arylation of phosphoryl-stabilized C-H acids, C-N, C-P bond forming reactions (substitution reactions) and in the reaction of phenylacetylene and bis(pinacolato)diboron (addition reaction). The complexes demonstrate fairly high catalytic activity and in some cases their efficiency is superior to that of the parent Cu(phen)(PPh3)Br (phen = phenanthroline).
Palladium-Catalyzed Reaction of Aryl Polyfluoroalkanesulfonates with O,O-Dialkyl Phosphonates
Lu, Xiyan,Zhu, Jingyang
, p. 726 - 727 (1987)
Arylphosphonates were synthesized by the reaction of aryl polyfluoroalkanesulfonates with O,O-dialkyl phpsphonates in the presence of triethylamine under palladium catalysis in good to excellent yield.
Novel approach to metal-induced oxidative phosphorylation of aromatic compounds
Khrizanforov,Strekalova,Kholin,Khrizanforova,Kadirov,Gryaznova,Budnikova
, p. 133 - 141 (2017)
We propose a new approach to the phosphorylation of benzenes bearing both electron withdrawing and electron donating substituents on the ring and some coumarins (coumarin, 6-methylcoumarin, 7-methylcoumarin) under the action of dialkyl H-phosphonate (RO)
Pd-catalyzed P-arylation of triarylantimony dicarboxylates with dialkyl H-phosphites without a base: Synthesis of arylphosphonates
Matsumura, Mio,Dong, Yuqiang,Kakusawa, Naoki,Yasuike, Shuji
, p. 130 - 133 (2015)
The reaction of triarylantimony diacetates [Ar3Sb(OAc)2] with dialkyl H-phosphites [H-PO(OR)2] in the presence of a Pd(PPh3)4 (5 mol%) catalyst led to the formation of arylphosphonates in moderate to excellent yield under base-free conditions. This reaction is the first example of carbon-phosphorus bond formation by using an organoantimony compound as a pseudo-halide.
The Palladium Acetate-Catalyzed Microwave-Assisted Hirao Reaction without an Added Phosphorus Ligand as a “Green” Protocol: A Quantum Chemical Study on the Mechanism
Keglevich, Gy?rgy,Henyecz, Réka,Mucsi, Zoltán,Kiss, Nóra Zs.
, p. 4322 - 4331 (2017)
It was proved by our experiments that on microwave irradiation, the mono- or bidentate phosphorus ligands generally applied in the palladium(II)-catalyzed P–C coupling reaction of aryl bromides and dialkyl phosphites or secondary phosphine oxides may be substituted by the excess of the >P(O)H reagent that exists under a tautomeric equilibrium. Taking into account that the reduction of the palladium(II) salt and the ligation of the palladium(0) so formed requires 3 equivalents of the P-species for the catalyst applied in a quantity of 5–10%, all together, 15–30% of the P-reagent is necessary beyond its stoichiometric quantity. In the coupling reaction of diphenylphosphine oxide, it was possible to apply diethyl phosphite as the reducing agent and as the P-ligand. The reactivities of the diethyl phosphite and diphenylphosphine oxide reagents were compared in a competitive reaction. The mechanism and the energetics of this new variation of the Hirao reaction of bromobenzene with Y2P(O)H reagents (Y=EtO and Ph) was explored by quantum chemical calculations. The first detailed study on simple reaction models justified our assumption that, under the conditions of the reaction, the trivalent form of the >P(O)H reagent may serve as the P-ligand in the palladium(0) catalyst, and shed light on the fine mechanism of the reaction sequence. The existence of the earlier described bis(palladium complex) {[H(OPh2P)2PdOAc]2} was refuted by high level theoretical calculations. This kind of complex may be formed only with chloride anions instead of the acetate anion. The interaction of palladium acetate and Y2P(O)H may result in only the formation of the [(HO)Y2P]2Pd complex that is the active catalyst in the Hirao reaction. The new variation of the Hirao reaction is of a more general value, and represents the greenest protocol, as there is no need for the usual P-ligands. Instead, the >P(O)H reagent should be used in an excess of up to 30%. Hence, the costs and environmental burdens may be decreased. (Figure presented.).
ELECTROCHEMICAL SYNTHESIS OF ARYL PHOSPHONATES
Nikitin, E. V.,Romakhin, A. S.,Parakin, O. V.,Romanov, G. V.,Kargin, Yu. M.,Pudovik, A. N.
, p. 566 - 569 (1983)
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Extraction of actinides by Tri-n-butyl phosphate derivatives: Effect of substituents
Annam, Suresh,Gopakumar, Gopinadhanpillai,Brahmmananda Rao,Sivaraman,Sivaramakrishna, Akella,Vijayakrishna, Kari
, p. 123 - 132 (2018)
Tri-n-butyl phosphate (TBP) is most extensively used extractant in the nuclear fuel cycle. The present work investigates the effect of substituents and their role in the basicity of organophosphorus extractant on the uptake of actinides. In this connection, we have synthesized six different analogues of TBP by altering one of its butoxy group. The synthesized TBP derivatives were well characterized and evaluated for their solvent extraction behavior towards U(VI), Th(IV), Pu(IV) and Am(III), as well as acid uptake as a function of nitric acid ranging from 0.01 to 6 M and the data provides the comparison of their extraction behavior with that of 30% (1.1 M) tri-n-butyl phosphate under identical conditions. It was observed that distribution coefficient values strongly depend on the nature and size of the substituents. The presence of electron donating groups enhances the uptake of the actinides and the distribution coefficient values were significantly larger as compared to that of TBP. In addition, the effect of sodium nitrate on the extraction of uranium and enthalpy of extraction were also studied and revealed that the extraction process was exothermic.
Microwave assisted P–C coupling reactions without directly added P-ligands
Henyecz, Réka,Huszár, Bianka,Keglevich, Gy?rgy,Mucsi, Zoltán
, (2021/12/24)
Our group introduced a green protocol for the Pd(OAc)2- or NiCl2-catalyzed P–C coupling reaction of aryl halides and various > P(O)H-compounds under MW conditions without directly added P-ligands. The reactivity of a few aryl derivatives in the Pd(OAc)2-catalyzed Hirao reaction was also studied. An induction period was observed in the reaction of bromobenzene and diphenylphosphine oxide. Finally, the less known copper(I)-promoted P–C coupling reactions were investigated experimentally. The mechanism was explored by quantum chemical calculations.
Microwave-assisted esterification of P-acids
ábrányi-Balogh, Péter,Harsági, Nikoletta,Keglevich, Gy?rgy,Kiss, Nóra Zsuzsa
, (2021/10/25)
The possibilities for the preparation of dialky phenylphosphonates were evaluated. On the one hand, the oxidation of phenyl-H-phosphinates gave the corresponding phenylphosphonic acid monoesters. On the other hand, phenylphosphonates may be prepared by MW-assisted direct esterification of phenylphosphonic acid. The reaction with alcohols was performed under MW irradiation in the presence of an ionic liquid as the catalyst. The second ester function was established by alkylating esterification carried out with alkyl halides in the presence of triethylamine under MW conditions.
Nickel- and Palladium-Catalyzed Cross-Coupling of Aryl Fluorosulfonates and Phosphites: Synthesis of Aryl Phosphonates
Zhang, Guofu,Wang, Jing,Guan, Chenfei,Zhao, Yiyong,Ding, Chengrong
, p. 810 - 813 (2021/02/01)
The synthesis of aryl phosphonates via nickel and palladium-catalyzed cross-coupling of aryl fluorosulfonates and phosphites is described. The products were obtained in good to excellent yields under mild conditions with broad functional group compatibility, employing either Pd(OAc)2 and DPEPhos or the readily available NiCl2(dme) and Xantphos as catalytic systems. Noteworthily, the present C(sp2)?P bond formation method could be applied to the direct conversion of phenols to the corresponding aryl phosphonates in one pot via reaction of phenols with SO2F2 and subsequent palladium-catalyzed cross-coupling.
