3095-33-8Relevant academic research and scientific papers
Efficient potassium hydroxide promoted P-arylation of aryl halides with diphenylphosphine
Chen, Jin,Dai, Bencai,Liu, Changchun,Shen, Zhihao,Zhou, Yang
, (2021/06/26)
A simple synthetic method of triarylphosphine compounds by KOH-promoted P-Arylation reaction of aryl halides with diphenylphosphine is presented. Notably, this transformation could smoothly proceed with high yields under transition-metal-free and mild reaction conditions. In addition, this protocol is valuable for industrial application due to the convenient operation and readily accessible aromatic halides. A possible explanation of the reaction mechanism was proposed based on the experimental data.
NiCl 2as a Cheap and Efficient Precatalyst for the Coupling of Aryl Fluorosulfonate and Phosphite/Phosphine Oxide
Yan, Wenjie,Zhou, Hongbo,Li, Haoyuan,Hu, Huimin,Yu, Ying,Guo, Shengmei,Cai, Hu
, p. 1453 - 1456 (2021/07/20)
Herein, NiCl 2is employed as a cheap precatalyst in the formation of C(sp 2)-P bond via cross-coupling reaction of phenol derivatives and phosphine oxides/phosphites. This catalytic system allows a variety of phenols with diverse functional groups to transform into phosphates with good yields. No additional additive is used in this reaction.
Copper-Catalyzed C?P Cross-Coupling of (Cyclo)alkenyl/Aryl Bromides and Secondary Phosphine Oxides with in situ Halogen Exchange
Stankevi?, Marek,Wo?nicki, Pawe?
supporting information, p. 3484 - 3491 (2021/07/22)
An efficient protocol for concurrent tandem halogen exchange/C?P cross-coupling of cycloalkenyl bromides and secondary phosphine oxides has been developed. The catalytic system is based on cheap and air-stable copper(I) iodide as the precatalyst, commercially available N,N’-dimethylethylenediamine as the ligand, and Cs2CO3 or K2CO3 as the base. The use of sodium iodide as an additive reduces the excessive use of organic bromides to near-stoichiometric by promoting the in situ transformation to the corresponding iodides. Diarylphosphine oxides undergo cycloalkenylation with 35–99 % yields and dicyclohexylphosphine oxide with 30–53 % yields. In the case of acyclic alkenyl bromides the cross-coupling products undergo conjugate addition of diphenylphosphine oxide and satisfying yields are observed only for internal olefins. In the case of aryl bromides satisfying yields (43–72 %) are observed only for sterically unhindered arenes or arenes possessing an ortho-directing group. Cycloalkenylphosphine oxides prepared in the cross-coupling reaction undergo base-catalyzed and base-promoted conjugate addition to give bis(phosphinoyl)cycloalkanes.
Preparation method of aromatic phosphine oxide compound
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Paragraph 0043-0045, (2021/10/20)
The invention relates to the field of organic synthesis, in particular to a preparation method of an aromatic phosphine oxide compound. The preparation method comprises the following steps: adding a P(O)-H compound, a fluoroaromatic compound and an alkali reagent into an organic solvent, conducting mixing, performing stirring for reaction, and carrying out cooling to obtain a mixed solution; and carrying out washing and extracting to obtain an organic phase, drying and distilling the organic phase, and performing column chromatography to obtain the aromatic phosphine oxide compound. The method is simple in reaction operation, only a proper amount of alkali needs to be added, special reaction conditions such as ligands, catalysts and additives are not needed, the reaction is simple and efficient, and good industrial application prospects are achieved.
Palladium-catalyzed C–P bond activation of aroyl phosphine oxides without the adjacent “anchoring atom”
Chen, Xingyu,Liu, Xiaoyan,Zhu, Hong,Wang, Zhiqian
, (2021/01/14)
A novel palladium-catalyzed decarbonylation of aroyl phosphine oxides to prepare phosphine oxides from carboxylic acids is developed. Without the adjacent “anchoring atom”, the challenging C–P bond activation is achieved in high selectivity. The disclosure of this reaction provides a new example of C–P bond activation and helps to extend the understanding of the property of C–P bond.
Mn-Catalyzed Electrooxidative Undirected C-H/P-H Cross-Coupling between Aromatics and Diphenyl Phosphine Oxides
Wang, Siyuan,Xue, Qilin,Guan, Zhipeng,Ye, Yayu,Lei, Aiwen
, p. 4295 - 4300 (2021/05/06)
C-P bonds are widely found in a great many bioactive compounds and functional molecules. Transition-metal-catalyzed dehydrogenative C-H/P-H cross-coupling plays a crucial part in C-P bond formation since it requires no pretreatment of substrates. Herein, we reported a Mn-catalyzed electrochemical intermolecular dehydrogenative cross-coupling between aryl C-H and diphenyl phosphine oxides. In undivided cells, a series of phosphorylation or diphosphorylation products could be obtained separately by adjusting the proportion of substrates. A catalytic amount of inexpensive Mn(II) salt was used, and no external chemical oxidants were needed in this process. A kinetic isotope effect experiment suggested that the C-H activation was not the rate-determining step.
Cu/Picolinamides-Catalyzed Coupling of (Hetero)aryl Halides with Secondary Phosphine Oxides and Phosphite?
Fang, Chao,Wei, Bangguo,Ma, Dawei
supporting information, p. 2957 - 2961 (2021/08/23)
Some 4-hydroxy-picolinic acid derived amides were revealed as more efficient ligands for Cu-catalyzed coupling of (hetero)aryl halides with secondary phosphine oxides and phosphites. Only 3—5 mol% CuI and ligands were required to ensure coupling with a number of (hetero)aryl bromides and iodides to complete at 120 oC in 10—20 h.
Controllable phosphorylation of thioesters: Selective synthesis of aryl and benzyl phosphoryl compounds
Xu, Kaiqiang,Liu, Long,Li, Zhaohui,Huang, Tianzeng,Xiang, Kang,Chen, Tieqiao
, p. 14653 - 14663 (2020/12/29)
The controllable phosphorylations of thioesters were developed. When the reaction was catalyzed by a palladium catalyst, aryl or alkenyl phosphoryl compounds were generated through decarbonylative coupling, while the benzyl phosphoryl compounds were produced through deoxygenative coupling when the reaction was carried out in the presence of only a base.
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.
Palladium-Catalyzed C-P Cross-Coupling between (Het)aryl Halides and Secondary Phosphine Oxides
Zakirova, Gladis G.,Mladentsev, Dmitrii Yu.,Borisova, Nataliya E.
, p. 2379 - 2386 (2019/05/24)
An efficient procedure for C-P bond formation via the palladium-catalyzed [Pd(OAc) 2 /dppf/Cs 2 CO 3 ] reaction between dichloroheterocycles and secondary phosphine oxides was developed. The steric and electronic properties of substituents were varied to establish the scope and limitations of the method developed. By applying these conditions, a variety of new heterocyclic compounds bearing two tertiary phosphine oxides were successfully synthesized in moderate to excellent yields. After adjustments to the reaction conditions [Pd(OAc) 2 /dippf/ t -BuOK], cross-coupling of secondary phosphine oxides with bulky (secondary or tertiary alkyl) substituents on the phosphorus atom was achieved. Extension of the methodology to monohalohetarenes and monohaloarenes was successfully carried out; once again, the steric and electronic properties of the halides were varied widely. The desired reaction occurred in all cases studied, giving high to excellent yields of product regardless of the nature and positions of substituents.
