1024-34-6Relevant academic research and scientific papers
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.
PALLADIUM-CATALYZED NEW CARBON-PHOSPHORUS BOND FORMATION
Hirao, Toshikazu,Masunaga, Toshio,Yamada, Naoto,Ohshiro, Yoshiki,Agawa, Toshio
, p. 909 - 913 (1982)
Dialkyl arylphosphonates are prepared by the palladium-catalyzed reaction of aryl bromides with dialkyl phosphite in the presence of triethylamine.The similar treatment of vinyl bromides gives dialkyl vinylphosphonates stereoselectively.
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).
Synthesis of diverse aromatic oxophosphorus compounds by the Michaelis-Arbuzov-type reaction of arynes
Yoshida, Suguru,Hosoya, Takamitsu
, p. 583 - 585 (2013)
Arynes, generated in situ from o-(trimethylsilyl)aryl triflates by treatment with a fluoride, have been shown to react efficiently with various alkoxyphosphines via a mechanism similar to the Michaelis-Arbuzov reaction. Diverse aromatic oxophosphorus compounds, including derivatives with an ortho-ester function, have become easily available from a common aryne precursor by this method.
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.
Reaction of trivalent phosphorus compounds with an Fe(III) complex in the presence of alcohol. Single electron transfer accompanied by a P-O bond formation
Yasui, Shinro,Itoh, Kenji,Tsujimoto, Munekazu,Ohno, Atsuyoshi
, p. 1019 - 1020 (1998)
Reactions of various types of trivalent phosphorus compounds with iron(III) complex in the presence of ethanol have been examined kinetically, showing that the single electron transfer from the former compounds to the latter is followed by rapid reaction of the resulting trivalent phosphorus radical cations with ethanol.
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)
Synthesis of phosphonates from phenylphosphonic acid and its monoesters
Henyecz, Réka,Kiss, Adrienn,Mórocz, Virág,Kiss, Nóra Zsuzsa,Keglevich, Gy?rgy
, p. 2642 - 2650 (2019)
Possibilities for the mono- and diesterification of phenylphosphonic acid were evaluated considering the microwave(MW)-assisted direct esterification, and the alkylating esterification. It was found that regarding the monoesterification, the reaction with 15-fold alcohol excess in the presence of [bmim][BF4] additive utilizing MWs is superior than the approach by alkylation. At the same time, for the conversion of the monoester intermediate to the diester, the reaction with alkyl halides in the presence of triethylamine as the base, again under MW irradiation, was found to be the method of choice. Phosphonates with both identical and different alkoxy groups were made available.
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.).
