25944-71-2Relevant articles and documents
New NLO stilbene derivatives bearing phosphonate ester electron-withdrawing groups
Belfield, Kevin D.,Chinna, Chandrasekhar,Schafer, Katherine J.
, p. 6131 - 6134 (1997)
The synthesis and characterization of a new class of electron donor-acceptor substituted stilbenes hearing a phosphonate ester as the electron-withdrawing functionality is described. Phosphorylation of aromatic rings was accomplished using Ni-catalyzed Arbuzov reactions, while Pd-catalyzed Heck-type coupling reactions were employed to construct the stilbene derivatives. Through determination of an electro-optic coefficient (r33), it was demonstrated that the phosphonate ester group is effective as an electron-withdrawing group for stilbene-based second-order NLO materials.
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.
Visible-light-mediated phosphonylation reaction: formation of phosphonates from alkyl/arylhydrazines and trialkylphosphites using zinc phthalocyanine
Hosseini-Sarvari, Mona,Koohgard, Mehdi
, p. 5905 - 5911 (2021/07/12)
In this work, we developed a ligand- and base-free visible-light-mediated protocol for the photoredox syntheses of arylphosphonates and, for the first time, alkyl phosphonates. Zinc phthalocyanine-photocatalyzed Csp2-P and Csp3-P bond formations were efficiently achieved by reacting aryl/alkylhydrazines with trialkylphosphites in the presence of air serving as an abundant oxidant. The reaction conditions tolerated a wide variety of functional groups.
Visible-Light-Induced Nickel-Catalyzed P(O)-C(sp2) Coupling Using Thioxanthen-9-one as a Photoredox Catalysis
Zhu, Da-Liang,Jiang, Shan,Wu, Qi,Wang, Hao,Chai, Lu-Lu,Li, Hai-Yan,Li, Hong-Xi
supporting information, p. 160 - 165 (2021/01/09)
An efficient method has been developed for photocatalytic P(O)-C(sp2) coupling of (hetero)aryl halides with H-phosphine oxides or H-phosphites under the irradiation of visible light or sunlight. The thioxanthen-9-one/nickel dual catalysis mediates this ph
A case of chain propagation: α-aminoalkyl radicals as initiators for aryl radical chemistry
Constantin, Timothée,Juliá, Fabio,Leonori, Daniele,Sheikh, Nadeem S.
, p. 12822 - 12828 (2020/12/29)
The generation of aryl radicals from the corresponding halides by redox chemistry is generally considered a difficult task due to their highly negative reduction potentials. Here we demonstrate that α-aminoalkyl radicals can be used as both initiators and chain-carriers for the radical coupling of aryl halides with pyrrole derivatives, a transformation often employed to evaluate new highly reducing photocatalysts. This mode of reactivity obviates for the use of strong reducing species and was also competent in the formation of sp2 C-P bonds. Mechanistic studies have delineated some of the key features operating that trigger aryl radical generation and also propagate the chain process.
Decarbonylative Phosphorylation of Carboxylic Acids via Redox-Neutral Palladium Catalysis
Liu, Chengwei,Ji, Chong-Lei,Zhou, Tongliang,Hong, Xin,Szostak, Michal
supporting information, p. 9256 - 9261 (2019/11/19)
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.
Nickel-Catalyzed Electrochemical Phosphorylation of Aryl Bromides
Bai, Ya,Liu, Nian,Wang, Shutao,Wang, Siyu,Ning, Shulin,Shi, Lingling,Cui, Lili,Zhang, Zhuoqi,Xiang, Jinbao
supporting information, p. 6835 - 6838 (2019/09/30)
A nickel-catalyzed electrochemical cross-coupling reaction of aryl bromides with dialkyl phosphites, ethyl phenylphosphinate, and diphenylphosphine oxide has been developed. This reaction utilizes a simple undivided cell with inexpensive carbon electrodes to synthesize aryl phosphonates, aryl phosphinates, and arylphosphine oxides at room temperature. This protocol provides a mild and efficient route for the construction of C-P bond in moderate to high yields with broad substrate scope.
Catalyst-free phosphorylation of aryl halides with trialkyl phosphites through electrochemical reduction
Wang, Shuai,Yang, Cheng,Sun, Shuo,Wang, Jianbo
supporting information, p. 14035 - 14038 (2019/11/25)
A catalyst-free electrochemical cross-coupling reaction of aryl halides with trialkyl phosphite has been developed. This reaction proceeds in an undivided cell with a low-cost Ni anode and a graphite cathode under mild and neutral conditions. A wide range of functional groups are well-tolerated and the phosphorylated product can be obtained on the gram scale, showing that this transformation has the potential to be a valuable method for the construction of aromatic carbon-phosphorus bonds.
Visible-Light-Mediated Metal-Free Synthesis of Aryl Phosphonates: Synthetic and Mechanistic Investigations
Lecroq, William,Bazille, Pierre,Morlet-Savary, Fabrice,Breugst, Martin,Lalevée, Jacques,Gaumont, Annie-Claude,Lakhdar, Sami
supporting information, p. 4164 - 4167 (2018/07/29)
This work describes a straightforward access to a large variety of aryl phosphonates by the simple combination of diaryliodonium salts with phosphites in the presence of a base and under visible-light illumination. The reaction proceeds smoothly, tolerates various functionalities, and was applied for the synthesis of pharmaceutically relevant compounds. Mechanistic investigations, including EPR, NMR, and DFT calculations, support the postulated reaction mechanism.
Decarbonylative Phosphorylation of Amides by Palladium and Nickel Catalysis: The Hirao Cross-Coupling of Amide Derivatives
Liu, Chengwei,Szostak, Michal
, p. 12718 - 12722 (2017/10/06)
Considering the ubiquity of organophosphorus compounds in organic synthesis, pharmaceutical discovery agrochemical crop protection and materials chemistry, new methods for their construction hold particular significance. A conventional method for the synthesis of C?P bonds involves cross-coupling of aryl halides and dialkyl phosphites (the Hirao reaction). We report a catalytic deamidative phosphorylation of a wide range of amides using a palladium or nickel catalyst giving aryl phosphonates in good to excellent yields. The present method tolerates a wide range of functional groups. The reaction constitutes the first example of a transition-metal-catalyzed generation of C?P bonds from amides. This redox-neutral protocol can be combined with site-selective conventional cross-coupling for the regioselective synthesis of potential pharmacophores. Mechanistic studies suggest an oxidative addition/transmetallation pathway. In light of the importance of amides and phosphonates as synthetic intermediates, we envision that this Pd and Ni-catalyzed C?P bond forming method will find broad application.
