3453-00-7Relevant academic research and scientific papers
Novel cobalt(0)- or magnesium-mediated approaches to β-ketophosphonates
Orsini, Fulvia,Di Teodoro, Emanuela,Ferrari, Marinella
, p. 1683 - 1688 (2002)
Two novel approaches to β-ketophosphonates, based on cobalt(0)- or magnesium-mediated reactions of α-halophosphonates with esters are described.
Construction of Dual-Active-Site Copper Catalyst Containing both Cu-N3 and Cu-N4 Sites
Xiong, Yu,Wang, Shibin,Chen, Wenxing,Zhang, Jian,Li, Qiheng,Hu, Han-Shi,Zheng, Lirong,Yan, Wensheng,Gu, Lin,Wang, Dingsheng,Li, Yadong
, (2021)
Clear recognition and rational construction of suitable active center for specific reaction is always of great significance in designing highly efficient catalysts. Herein, a dual-active-site copper catalyst (DAS-Cu) containing both Cu-N3 and Cu-N4 sites is reported. Such catalysts show extremely high catalytic performance (yield: up to 97%) toward oxyphosphorylation of alkenes, while catalysts with single active site (Cu-N3 or Cu-N4) are chemically inert in this reaction. Combined with theoretical and experimental results, the different roles of two different Cu active sites in this reaction are further identified. Cu-N3 site captures the oxygen and trigger further oxidizing process, while Cu-N4 site provides moderate adsorption sites for the protection of phosphonyl radicals. This work deeply discloses the significant cooperated role with two single-atomic sites in one catalytic active center and brings up a valuable clue for the rational design of better-performing heterogeneous catalyst.
Synthesis and antiproliferative evaluation of new zampanolide mimics
Chen, Guanglin,Patanapongpibul, Manee,Jiang, Ziran,Zhang, Qiang,Zheng, Shilong,Wang, Guangdi,White, James D.,Chen, Qiao-Hong
, p. 3830 - 3844 (2019)
(?)-Zampanolide is a marine microtubule-stabilizing macrolide that has been shown by in vitro experiments to be a promising anticancer lead compound. Through its unique covalent-binding with β-tubulin, zampanolide exhibits cytotoxic potency towards multi-drug resistant cancer cells that is superior to paclitaxel. However, the limited availability of zampanolide impedes its further in vivo evaluation as a viable drug candidate. Zampanolide is envisioned to become more drug-like if its chemically fragile side chain can be stabilized; hence, this project aims to develop mimics of zampanolide with a stable side chain using straightforward synthetic methods. To this end, twelve novel zampanolide mimics (51-62) with conjugated and planar side chains have been synthesized via a 24-step sequence for each mimic from commercially available 2-butyn-1-ol as starting material. A Horner-Wadsworth-Emmons reaction incorporates the α,β-unsaturated ketone side chain and also closes the core macrocycle. WST-1 cell proliferation assays in three docetaxel-sensitive and two docetaxel-resistant human prostate cancer cell models confirm that a suitably designed side chain can serve as a bioisostere for the N-acyl hemiaminal side chain in zampanolide. Mimic 52 with a 17R chiral center was identified as the optimal candidate with IC50 values of 0.29-0.46 μM against both docetaxel-sensitive (PC-3 and DU145) and docetaxel-resistant prostate cancer cell lines (PC-3/DTX and DU145/DTX). Zampanolide mimic 52 exhibited equivalent antiproliferative potency towards both docetaxel-sensitive and docetaxel-resistant cell lines, with relative resistance in the range of 0.9-1.6.
Synthesis of 2-oxophosphorindolines: Via the copper-catalyzed intramolecular aromatic C-H insertion of diazophosphonamidates
Huang, Peipei,Xu, Jiaxi
, p. 63736 - 63748 (2016)
An efficient synthetic method for 2-ethoxy-2-oxophosphorindolines, benzo-γ-phospholactams, has been successfully achieved through the copper-catalyzed intramolecular aromatic C-H insertion of diazophosphonamidates with up to 97% yield. The current method has advantages of mild and clean conditions, and an inexpensive catalyst.
Direct and straightforward transfer of C1 functionalized synthons to phosphorous electrophiles for accessinggem-P-containing methanes
Touqeer, Saad,Ielo, Laura,Miele, Margherita,Urban, Ernst,Holzer, Wolfgang,Pace, Vittorio
supporting information, p. 2425 - 2429 (2021/04/02)
The direct transfer of different α-substituted methyllithium reagents to chlorinated phosphorous electrophiles of diverse oxidation state (phosphates, phosphine oxides and phosphines) is proposed as an effective strategy to synthesize geminal P-containing
Copper-Catalyzed Microwave-Expedited Oxyphosphorylation of Alkynes with Diethyl Phosphite and t-Butyl Hydroperoxide Synthesis of Densely Functionalized Phosphonylated Indenones
Maciás-Benítez, Pablo,Sierra-Padilla, Alfonso,Tenorio, Manuel J.,Moreno-Dorado, F. Javier,Guerra, Francisco M.
, p. 16409 - 16424 (2021/11/16)
Treatment of alkynes with diethyl phosphite and t-butyl hydroperoxide in the presence of [Cu(MeCN)4]BF4 under microwave irradiation produced the oxyphosphorylation of the triple bond, giving rise to the corresponding β-ketophosphonates in moderate-to-good yields. When the triple bond was conjugated to a carbonyl group bearing an aromatic ring, it led to the cyclization of the resulting ketone intermediate, producing eventually different phosphonylated indenones.
Copper ferrite nanoparticles catalyzed formation of β-Ketophosphonates via oxyphosphorylation of styrenes with H-phosphonates: A DFT study on UV–vis absorption spectra
Azaryan, Reza,Daneshfar, Maryam,Moghaddam, Firouz Matloubi,Pirat, Jean-Luc
, (2020/04/21)
Typical copper ferrite nanoparticles (CuFe2O4) were used as a catalyst for one-pot synthesis of β-ketophosphonates via the reaction of alkenes with H-phosphonates under conventional heating conditions. The catalyst was prepared by using the coprecipitation method and was analyzed by physiochemical techniques. By using this catalyst system, several types of useful and new β-ketophosphonate products were obtained in very good to excellent yields under optimized reaction conditions in a novel way. Furthermore, the catalyst is recyclable and reusable from the reaction.
Access to chiral α-substituted-β-hydroxy arylphosphonates enabled by biocatalytic dynamic reductive kinetic resolution
Chen, Fener,Huang, Zedu,Li, Zihan,Tao, Yuan,Wang, Zexu,Wu, Xiaofan,Yu, Xiaomin,Zeng, Yiping
supporting information, p. 2672 - 2677 (2020/04/17)
Ketoreductase (KRED)-catalyzed dynamic reductive kinetic resolution (DYRKR) of α-substituted-β-keto arylphosphonates was developed as a generic and stereoselective approach to synthesize chiral α-substituted-β-hydroxy arylphosphonates, with moderate-to-excellent isolated yield (up to 96%), good-to-excellent diastereoselectivity (up to >99 : 99% ee) being achieved.
Iron-Catalyzed and Air-Mediated C(sp3)?H Phosphorylation of 1,3-Dicarbonyl Compounds Involving C?C Bond Cleavage
Ou, Yingcong,Huang, Yuanting,Liu, Yu,Huo, Yanping,Gao, Yang,Li, Xianwei,Chen, Qian
supporting information, p. 5783 - 5787 (2020/11/30)
A C(sp3)?H phosphorylation has been achieved via the iron-catalyzed cross-coupling reactions between 1,3-dicarbonyl compounds and P(O)?H compounds involving C?C bond cleavages with air as the oxidant. This transformation provides a straightforward way to construct C(sp3)?P bonds, leading to the formation of β-ketophosphine oxides in up to 93% yield with good functional group tolerance. (Figure presented.).
Bivalent copper complex containing diphosphine ortho-position carborane ligand, preparation method and application thereof
-
Paragraph 0029; 0033-0036, (2020/09/16)
The invention relates to a bivalent copper complex containing a diphosphine ortho-position carborane ligand, a preparation method and application thereof. The copper complex is prepared by the following method of: adding an n-BuLi solution dropwise into an ortho-position carborane o-C2B10H12 solution, and carrying out stirring reaction, then adding halogenated phosphine for continuous reaction, adding copper acetate Cu(OAc)2 into the reaction system for continuous reaction, after the reaction is finished, performing separating to obtain the diphosphine ortho-position carborane ligand, and applying the copper complex to catalytic synthesis of a beta-carbonyl phosphine oxide compound. Compared with the prior art, the synthesis process has excellent selectivity and high yield, the copper complex can catalyze alpha-haloketone and phosphite to react to synthesize the beta-carbonyl phosphine oxide compound under the room temperature condition, and the reaction is efficient, green and environmentally friendly.
