65442-22-0Relevant academic research and scientific papers
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.
Palladium-catalyzed one-pot phosphorylation of phenols mediated by sulfuryl fluoride
Zhang, Yiyuan,Chen, Wanting,Tan, Tingting,Gu, Yuang,Zhang, Shuning,Li, Jie,Wang, Yan,Hou, Wei,Yang, Guang,Ma, Peixiang,Xu, Hongtao
, p. 4588 - 4591 (2021/05/17)
We report a general palladium-catalyzed one-pot procedure for the synthesis of phosphonates, phosphinates and phosphine oxides from phenols mediated by sulfuryl fluoride. It features mild conditions, broad substrate scope, high functionality tolerance and water insensitivity. The utility of this procedure has been well demonstrated by gram-scale synthesis, sequential synthesis of click chemistry building blocks, late-stage decoration of drugs and natural products and on-DNA synthesis of phosphine oxide for a DNA-encoded library (DEL).
Photoinduced transition-metal and external photosensitizer free cross-coupling of aryl triflates with trialkyl phosphites
Dou, Qian,Geng, Li,Cheng, Bin,Li, Chao-Jun,Zeng, Huiying
supporting information, p. 8429 - 8432 (2021/09/02)
Photoinduced phosphonation of aryl triflates with trialkyl phosphites via a tandem single-electron-transfer, C-O bond cleavage and Arbuzov rearrangement process in the absence of transition-metal and external photosensitizer is reported herein. The protoc
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.
Ar-P bond construction by the Pd-catalyzed oxidative cross-coupling of arylsilanes with H-phosphonates via C-Si bond cleavage
Luo, Haiqing,Liu, Haidong,Chen, Xingwei,Wang, Keke,Luo, Xuzhong,Wang, Kejun
supporting information, p. 956 - 958 (2017/01/17)
A novel and efficient methodology that allows for the construction of Ar-P bonds via the Pd-catalyzed oxidative cross-coupling reaction of various arylsilanes with H-phosphonates leading to valuable arylphosphonates has been developed.
Visible-Light photo-Arbuzov reaction of aryl bromides and trialkyl phosphites yielding aryl phosphonates
Shaikh, Rizwan S.,Düsel, Simon J.S.,K?nig, Burkhard
, p. 8410 - 8414 (2018/05/23)
Aryl phosphonates are functional groups frequently found in pharmaceutical and crop protection agents. For their synthesis via C?P bond formation typically transition-metal-catalyzed reactions are used. We report a visible-light photo-Arbuzov reaction as an efficient, mild, and metal-free alternative. Rhodamine 6G (Rh.6G) is used as the photocatalyst, generating aryl radicals under blue light. Coupling of the radicals with a wide range of trivalent phosphites gives aryl phosphonates in good to very good isolated yields. The mild reaction conditions allow the introduction of a phosphonate group into complex and sensitive pharmaceutically active molecules such as benzodiazepams and nicergoline by the activation of a carbon?halogen bond.
PROCESS FOR PREPARATION OF ARYL PHOSPHOROUS COMPOUNDS
-
Paragraph 0056-0057, (2015/08/04)
The present invention relates to cost effective, transition-metal-free one pot process for the preparation of aryl phosphorous compounds of formula (I). Particularly, the present invention provides a process for C—P bond formation. In particular, the invention relates to mild fluoride induced generation of aryne species in situ which allows P—C bond formation to obtain aryl phosphorous compounds of formula (I) under mild condition.
