799-55-3Relevant academic research and scientific papers
Visible-Light Driven C-P Bond Formation with Recyclable Carbon Nitride Photocatalyst
Guo, Wusheng,Liu, Yang
, (2022/05/12)
The development of metal-free chemical process with recyclable heterogeneous catalyst under ambient conditions is highly desired in industrial production, especially for pharmaceutical purpose. We herein reported the efficient synthesis of pharmaceuticall
Aryltrimethylammonium Tetrafluoroborates in Nickel-Catalyzed C–P Bond-Forming Reactions
Li, Chun Jing
, p. 954 - 960 (2021/07/22)
Abstract: The first nickel-catalyzed phosphorylation of aryltrimethylammonium tetrafluoroborates with the formation of C–P bond instead of C–N has been developed. Starting from easily available and inexpensive aromatic amines, a variety of important arylphosphonates have been synthesized in moderate to excellent yields.
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 semi-heterogeneous black TiO2/nickel dual catalytic C (sp2)-P bond formation toward aryl phosphonates
Koohgard, Mehdi,Karimitabar, Haniehsadat,Hosseini-Sarvari, Mona
supporting information, p. 17147 - 17151 (2020/12/28)
The combination of black TiO2 nanoparticles (NPs) with a nickel catalyst provides a low-cost, sustainable, and reusable alternative dual catalytic system to a homogeneous counterpart (noble metals). This black TiO2-photoredox/nickel dual catalytic system has efficiently driven C-P bond formation between aryl iodides and diarylphosphine oxides under visible light, providing good to excellent yields as well as tolerating a variety of functional groups. The practical application of this semi-heterogeneous protocol has been highlighted by a sunlight experiment, a gram-scale reaction, and a reusability test.
A Track-Based Molecular Synthesizer that Builds a Single-Sequence Oligomer through Iterative Carbon-Carbon Bond Formation
McTernan, Charlie T.,De Bo, Guillaume,Leigh, David A.
supporting information, p. 2964 - 2973 (2020/11/02)
We report an artificial molecular machine that moves along a track, iteratively joining building blocks to form an oligomer of single sequence with a continuous backbone of carbon-carbon bonds. The rotaxane features a macrocycle bearing an aldehyde-terminated chain and an axle containing different phosphonium ylides separated by rigid spacers. Each ylide is large enough to block the passage of the macrocycle, trapping the ring between the stopper at the terminus of original threading and the next ylide along the track. Once a building block is reachable, it is removed from the track through a Wittig reaction that adds it to the terminus of the growing chain. Operation on a four-barrier tetra(phosphonium salt) track produces a tetra(diphenylpropane) of single sequence linked through alkene bonds. The prototype extends the principle for molecular machines that build polymers by moving along tracks to the synthesis of sequence-encoded chains with continuous carbon backbones. Sequence is crucial in the molecular world. Proteins are built from a common set of 20 amino acids, but different sequences afford materials as diverse as snake venom, muscle, and spider silk. However, the synthesis of artificial sequence polymers remains challenging. Biology uses molecular machines (e.g., ribosomes) for such tasks, inspiring the invention of artificial systems that move along tracks, picking off and joining building blocks in sequence. To date, such small-molecule machines have used amide formation to join building blocks, the same bonds the ribosome uses to make peptides. Here, we report on the design, synthesis, and operation of a track-based molecular machine that assembles a single-sequence oligomer with a continuous backbone of carbon-carbon bonds. This new class of de novo molecular synthesizer utilizes chemistry and reactivity patterns unavailable to biological machines. The long-term goal is for such molecular assemblers to ultimately be able to play significant roles in molecular construction. Molecular machines, such as ribosomes, are ubiquitous in biology. These natural systems are inspiring artificial systems that move along tracks, picking off and joining building blocks in sequence. To date, such small-molecule machines have used amide formation to connect building blocks, much like the ribosome. Here, the design, synthesis, and operation of a track-based molecular machine that iteratively forms a continuous backbone of carbon-carbon bonds is described. This new class of de novo molecular synthesizer utilizes chemistry and reactivity patterns unavailable to biological machines.
Photoinduced Transition-Metal-Free Cross-Coupling of Aryl Halides with H-Phosphonates
Zeng, Huiying,Dou, Qian,Li, Chao-Jun
supporting information, p. 1301 - 1305 (2019/02/19)
Photoinduced transition-metal- and photosensitizer-free cross-coupling of aryl halides (including Ar-Cl, Ar-Br, and Ar-I) with H-phosphonates (including dialkyl phosphonates and diarylphosphine oxides) is reported. Various functional groups were tolerated, including ester, methoxy, dimethoxy, alkyl, phenyl, trifluoromethyl, and heterocyclic compounds. This simple and green strategy provides a practical pathway to synthesize arylphosphine oxides.
Flame retardant polycyanurate thermosets from the cyanate esters of triphenylphosphine oxide
Davis, Matthew C.,Garrison, Michael D.,Ghiassi, Kamran B.,Groshens, Thomas J.,Redeker, Neil D.
, p. 1100 - 1110 (2018/03/21)
Three cyanate esters containing phosphorus are synthesized in good overall yields starting from bromoanisoles. Di- and tricyanates with meta configuration are most stable while para is less so. The para dicyanate ester isomer is particularly affected by water from the atmosphere. The meta dicyanate ester 2 has good thermal properties with glass transition at 268 °C and char yield of 65% in air at 600 °C. All three phosphorus-containing cyanate esters are low flammability in an open flame. They make highly combustible cyanate esters resins less flammable simply by blending. Mixing 10 wt% dicyanate ester 2 into bisphenol A or E dicyanate esters makes them rate V-0. Published 2018.? J. Polym. Sci., Part A: Polym. Chem. 2018, 56, 1100–1110.
Synthesis method of carbonate modified fluoride-free organic phosphine ligand
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Paragraph 0028; 0029; 0038, (2017/08/28)
The invention relates to the field of organic synthesis and provides a synthesis method of a carbonate modified fluoride-free organic phosphine ligand. The synthesis method comprises the following steps: preparing a Grignard reagent from the raw material p-bromoanisole or derivative thereof; enabling the Grignard reagent to react with a phosphorus source to generate a skeleton structure molecule with triphenylphosphine; and performing oxidation, demethylation, nucleophilic substitution and reduction to obtain a target molecular structure. The synthesis method has the following effects and benefits: a novel carbon dioxide-philic organic phosphine ligand is synthesized, the solubility of the phosphine ligand in supercritical CO2 is increased, and application of a fluoride-free phosphine ligand organic metal catalyst in supercritical CO2 is realized. Moreover, the organic carbonate compound is insoluble in a weakly (non-) polar organic solvent (such as alkane compounds), the property enables a phase splitting function of the carbonate modified fluoride-free organic phosphine ligand in the reaction system, and the recycling and reusing of the catalyst are realized.
Preparation of organophosphorus compounds from P-H compounds using o-(trimethylsilyl)aryl triflates as aryne precursors
Yang, Guoqiang,Shen, Chaoren,Quan, Mao,Zhang, Wanbin
, p. 333 - 337 (2015/12/30)
An efficient method was developed for the synthesis of a variety of arylphosphorus compounds from P-H compounds using o-(trimethylsilyl)aryl triflates as aryne precursors. The reaction provides a practical preparation of various arylphosphorus compounds via aryne intermediates utilizing diarylphosphine oxides and dialkyl phosphites as the nucleophiles.
Copper-Catalyzed Addition of H-P(O) Bonds to Arynes
Chen, Qian,Yan, Xinxing,Wen, Chunxiao,Zeng, Jiekun,Huang, Yulin,Liu, Xingguo,Zhang, Kun
, p. 9476 - 9482 (2016/10/14)
An efficient P-arylation of secondary phosphine oxides has been achieved through the ligand-free copper-catalyzed addition of H-P(O) bonds to in situ generated arynes at room temperature. This transformation provides a straightforward route to the formation of the aryl-P bond with wide functional group compatibility, which produces arylphosphine oxides in up to 99% yield.
