- CuSO4/Al2O3 as a new effective and recyclable catalyst for the arylation of dialkyl phosphites
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A new effective recycled catalyst CuSO4/Al2O 3, which performs the phosphorylation of aryl halides and bromostyrene, was proposed.
- Karlstedt,Anokhin,Beletskaya
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Read Online
- Product selectivities and third-order rate laws for solvolyses of ethyl phenylphosphonochloridate in aqueous alcohols
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Rate constants and product selectivities (S) for solvolyses of ethyl phenylphosphonochloridate [PhP(=O)OEtCl] in aqueous ethanol and methanol at 0°C are reported; S = ([ester product]/[acid product]) x ([water]/[alcohol solvent]). The results show trends
- Bentley, T. William,Ebdon, David N.
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Read Online
- An intramolecular Arbuzov rearrangement initiated by anodic oxidation
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Dialkyl phenylphosphonite PhP(OR)2 (R = Et, Me) undergoes an intramolecular Arbuzov rearrangement upon electrolysis at an anode in acetonitrile under an oxygen atmosphere to yield alkyl alkylphenylphosphinate PhRP(=O)(OR). The results here suggest that the rearrangement takes place through a radical-chain mechanism initiated by anodic oxidation of the phosphonite to the corresponding cation radical.
- Yasui, Shinro,Shioji, Kosei,Tsujimoto, Munekazu,Ohno, Atsuyoshi
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Read Online
- Heterogeneous Organophosphate Ethanolysis: Degradation of Phosphonothioate Neurotoxin by a Supported Molybdenum Peroxo Polymer
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A polystyrene-supported molybdenum peroxo material [Mo-Y(s)] was applied toward the oxidative degradation of the organophosphate neurotoxin O,S-diethylphenyl phosphonothioate (1) through ethanolysis. In addition to the operational advantages of the heterogeneous reactivity, oxidative ethanolysis with a 10-fold excess of hydrogen peroxide yields only P-S bond scission to produce diethylphenyl phosphonate and ethyl sulfate. This is the first report of a molybdenum solid support that promotes the degradation of sulfur-containing organophosphate with the turnover benefits of heterogeneous catalysis. The activation parameters of 1 ethanolysis by Mo-Y(s) (Ea = 57 ± 6 kJ/mol and ΔS? = -124 ± 21 J/mol·K) and by the model compound oxodiperoxo(pyridine-2-carboxylato)molybdate(VI) bis(pyridine-2-carboxylic acid) monohydrate (3; Ea = 55 ± 5 kJ/mol and ΔS? = -154 ± 15 J/mol·K) are almost identical for the oxidation of thioanisole by 3. This suggests that the rate-determining step for 1 ethanolysis is sulfur oxidation to form an intermediate phosphonothioate S-oxide, which subsequently undergoes nucleophilic attack by the ethanol solvent to form diethylphenyl phosphonate and ethyl sulfate. Evidence for the formation of this S-oxide intermediate and the postulated ethanolysis mechanism is provided.
- Kuo, Louis Y.,Bennett, Andrew,Miao, Qianli
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Read Online
- Evaluation of transition metal catalysts in electrochemically induced aromatic phosphonation
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Voltammetry provides important information on the redox properties of catalysts (transition metal complexes of Ni, Co, Mn, etc.) and their activity in electrocatalytic reactions of aromatic C-H phosphonation in the presence of a phosphorus precursor, for
- Strekalova, Sofia,Khrizanforov, Mikhail,Budnikova, Yulia
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Read Online
- New method of metal-induced oxidative phosphorylation of benzene
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A new approach to phosphorylation of benzene with diethyl phosphite is suggested, which is based on the electrocatalytic oxidation of a mixture of benzene and diethyl phosphite (1 : 1) under mild conditions (room temperature, normal pressure) in the presence of bimetallic catalytic systems MnII/CoIIL (MnSO4/CoCl2dmphen or MnCl2/CoCl2bipy). This method gives diethyl phenylphosphonate in high yield (up to 90%) and practically 100% conversion of the phosphite.
- Khrizanforov,Strekalova,Gryaznova,Khrizanforova,Budnikova, Yu. H.
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Read Online
- Direct Near Infrared Light–Activatable Phthalocyanine Catalysts
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The high penetration of near-infrared (NIR) light makes it effective for use in selective reactions under light-shielded conditions, such as in sealed reactors and deep tissues. Herein, we report the development of phthalocyanine catalysts directly activa
- Katsurayama, Yoshino,Ikabata, Yasuhiro,Maeda, Hajime,Segi, Masahito,Nakai, Hiromi,Furuyama, Taniyuki
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supporting information
(2021/12/22)
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- Controlling Chemoselectivity of Catalytic Hydroboration with Light
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The ability to selectively react one functional group in the presence of another underpins efficient reaction sequences. Despite many designer catalytic systems being reported for hydroboration reactions, which allow introduction of a functional handle fo
- Bergamaschi, Enrico,Chen, Yi-Kai,Hohenadel, Melissa,Lunic, Danijela,McLean, Liam A.,Teskey, Christopher J.
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supporting information
(2022/01/13)
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- Microwave assisted P–C coupling reactions without directly added P-ligands
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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.
- Henyecz, Réka,Huszár, Bianka,Keglevich, Gy?rgy,Mucsi, Zoltán
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- Fe-MIL-101 modified by isatin-Schiff-base-Co: a heterogeneous catalyst for C-C, C-O, C-N, and C-P cross coupling reactions
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A metal-organic framework functionalized with a cobalt-complex is preparedviapost-synthetic modification of Fe-MIL-101-NH2. Initially, Fe-MIL-101-NH2reacted with isatin to produce Fe-MIL-101-isatin-Schiff-base, which can anchor the cobalt by the addition of cobalt acetate. The resulting MOF-Co catalyst is characterized by employing multiple techniques. This new modified MOF acts as a heterogeneous and recyclable catalyst for efficient Ullmann, Buchwald-Hartwig, Hirao, Hiyama and Mizoroki-Heck cross-coupling reactions of several aryl halides/phenylboronic acid/phenyltosylate with phenols, anilines/heterocyclic amines, triethyl phosphite, triethoxyphenylsilane and alkenes and generates the expected coupling products in good to high yields.
- Farrokhi, Alireza,Rouzifar, Majid,Sansano, José Miguel,Sobhani, Sara
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p. 19963 - 19976
(2021/11/12)
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- Photoinduced transition-metal and external photosensitizer free cross-coupling of aryl triflates with trialkyl phosphites
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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
- Dou, Qian,Geng, Li,Cheng, Bin,Li, Chao-Jun,Zeng, Huiying
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supporting information
p. 8429 - 8432
(2021/09/02)
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- Microwave-assisted esterification of P-acids
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The possibilities for the preparation of dialky phenylphosphonates were evaluated. On the one hand, the oxidation of phenyl-H-phosphinates gave the corresponding phenylphosphonic acid monoesters. On the other hand, phenylphosphonates may be prepared by MW-assisted direct esterification of phenylphosphonic acid. The reaction with alcohols was performed under MW irradiation in the presence of an ionic liquid as the catalyst. The second ester function was established by alkylating esterification carried out with alkyl halides in the presence of triethylamine under MW conditions.
- ábrányi-Balogh, Péter,Harsági, Nikoletta,Keglevich, Gy?rgy,Kiss, Nóra Zsuzsa
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- Visible-light-mediated phosphonylation reaction: formation of phosphonates from alkyl/arylhydrazines and trialkylphosphites using zinc phthalocyanine
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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.
- Hosseini-Sarvari, Mona,Koohgard, Mehdi
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p. 5905 - 5911
(2021/07/12)
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- Non-innocent Radical Ion Intermediates in Photoredox Catalysis: Parallel Reduction Modes Enable Coupling of Diverse Aryl Chlorides
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We describe a photocatalytic system that elicits potent photoreductant activity from conventional photocatalysts by leveraging radical anion intermediates generated in situ. The combination of an isophthalonitrile photocatalyst and sodium formate promotes diverse aryl radical coupling reactions from abundant but difficult to reduce aryl chloride substrates. Mechanistic studies reveal two parallel pathways for substrate reduction both enabled by a key terminal reductant byproduct, carbon dioxide radical anion.
- Chernowsky, Colleen P.,Chmiel, Alyah F.,Wickens, Zachary K.,Williams, Oliver P.,Yeung, Charles S.
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supporting information
p. 10882 - 10889
(2021/07/31)
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- Tf2O/DMSO-Promoted P-O and P-S Bond Formation: A Scalable Synthesis of Multifarious Organophosphinates and Thiophosphates
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A Tf2O/DMSO-based system for the dehydrogenative coupling of a wide range of alcohols, phenols, thiols, and thiophenols with diverse phosphorus reagents has been developed. This metal- and strong-oxidant-free strategy provides a facile approach to a great variety of organophosphinates and thiophosphates. The simple reaction system, good functional-group tolerance, and broad substrate scope enable the application of this method to the modification of natural products and the direct synthesis of bioactive molecules and flame retardants.
- Shen, Jian,Li, Qi-Wei,Zhang, Xin-Yue,Wang, Xue,Li, Gui-Zhi,Li, Wen-Zuo,Yang, Shang-Dong,Yang, Bin
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supporting information
p. 1541 - 1547
(2021/04/05)
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- Electrochemical Activation of Diverse Conventional Photoredox Catalysts Induces Potent Photoreductant Activity**
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Herein, we disclose that electrochemical stimulation induces new photocatalytic activity from a range of structurally diverse conventional photocatalysts. These studies uncover a new electron-primed photoredox catalyst capable of promoting the reductive cleavage of strong C(sp2)?N and C(sp2)?O bonds. We illustrate several examples of the synthetic utility of these deeply reducing but otherwise safe and mild catalytic conditions. Finally, we employ electrochemical current measurements to perform a reaction progress kinetic analysis. This technique reveals that the improved activity of this new system is a consequence of an enhanced catalyst stability profile.
- Chernowsky, Colleen P.,Chmiel, Alyah F.,Wickens, Zachary K.
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p. 21418 - 21425
(2021/08/25)
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- Selective esterification of phosphonic acids
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Here, we report straightforward and selective synthetic procedures for mono-and diesteri-fication of phosphonic acids. A series of alkoxy group donors were studied and triethyl orthoacetate was found to be the best reagent as well as a solvent for the performed transformations. An important temperature effect on the reaction course was discovered. Depending on the reaction temperature, mono-or diethyl esters of phosphonic acid were obtained exclusively with decent yields. The sub-strate scope of the proposed methodology was verified on aromatic as well as aliphatic phosphonic acids. The designed method can be successfully applied for small-and large-scale experiments without significant loss of selectivity or reaction yield. Several devoted experiments were performed to give insight into the reaction mechanism. At 30?C, monoesters are formed via an intermediate (1,1-diethoxyethyl ester of phosphonic acid). At higher temperatures, similar intermediate forms give diesters or stable and detectable pyrophosphonates which were also consumed to give diesters.31P NMR spectroscopy was used to assign the structure of pyrophosphonate as well as to monitor the reaction course. No need for additional reagents and good accessibility and straightforward purification are the important aspects of the developed protocols.
- Trzepizur, Damian,Brodzka, Anna,Koszelewski, Dominik,Ostaszewski, Ryszard
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- Selective hydrolysis of phosphorus(v) compounds to form organophosphorus monoacids
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An azide and transition metal-free method for the synthesis of elusive phosphonic, phosphinic, and phosphoric monoacids has been developed. Inert pentavalent P(v)-compounds (phosphonate, phosphinate, and phosphate) are activated by triflate anhydride (Tf2O)/pyridine system to form a highly reactive phosphoryl pyridinium intermediate that undergoes nucleophilic substitution with H2O to selectively deprotect one alkoxy group and form organophosphorus monoacids.
- Ash, Jeffrey,Cordero, Paula,Huang, Hai,Kang, Jun Yong
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p. 6007 - 6014
(2021/07/21)
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- High performance liquid phase continuous automatic production and co-production technology of organic phosphine compound
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The invention relates to the field of photocuring functional new material chemicals, and discloses a high performance liquid phase streamline type continuous automatic production technology of an acylphosphine oxide organic phosphine compound for the first time, which not only can produce a single specific target product, but also can co-produce a product mixture of two or more than two of the products of the type. The process technology has outstanding low-cost economic competitiveness and environment-friendly characteristics for large-scale manufacturing of target products. The target product comprises sym-trimethylbenzoyl diphenyl phosphine oxide (also known as 2, 4, 6-trimethylbenzoyl diphenyl phosphine oxide, trade name TPO), sym-trimethylbenzoyl phenyl ethyl phosphonate (trade name TPO-L) and structural analogues thereof, and a mixture of the sym-trimethylbenzoyl diphenyl phosphine oxide and the sym-trimethylbenzoyl phenyl ethyl phosphonate. The organic phosphine compound is an olefinic bond-containing (C=C) unsaturated radiation polymerization system photoinitiator and/or flame retardant and the like with wide application.
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Paragraph 0075-0076
(2021/05/12)
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- METHOD FOR PRODUCING PHOSPHOESTER COMPOUND
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PROBLEM TO BE SOLVED: To provide a method whereby, a phosphate compound selected from the group consisting of orthophosphoric acid, phosphonic acid, phosphinic acid, and anhydrides of them is used as raw material and, by one stage reaction, a corresponding phosphoester compound is produced. SOLUTION: To an aqueous solution of a phosphate compound, added is an organic silane or siloxane compound having an alkoxy group or an aryloxy group, and the mixture is subjected to a heating reaction, thereby producing a corresponding phosphoester compound without requiring a catalyst. SELECTED DRAWING: None COPYRIGHT: (C)2021,JPOandINPIT
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Paragraph 0023; 0029-0031
(2021/09/27)
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- Radical Chain Reduction via Carbon Dioxide Radical Anion (CO2?-)
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We developed an effective method for reductive radical formation that utilizes the radical anion of carbon dioxide (CO2?-) as a powerful single electron reductant. Through a polarity matched hydrogen atom transfer (HAT) between an electrophilic radical and a formate salt, CO2?- formation occurs as a key element in a new radical chain reaction. Here, radical chain initiation can be performed through photochemical or thermal means, and we illustrate the ability of this approach to accomplish reductive activation of a range of substrate classes. Specifically, we employed this strategy in the intermolecular hydroarylation of unactivated alkenes with (hetero)aryl chlorides/bromides, radical deamination of arylammonium salts, aliphatic ketyl radical formation, and sulfonamide cleavage. We show that the reactivity of CO2?- with electron-poor olefins results in either single electron reduction or alkene hydrocarboxylation, where substrate reduction potentials can be utilized to predict reaction outcome.
- Hendy, Cecilia M.,Smith, Gavin C.,Xu, Zihao,Lian, Tianquan,Jui, Nathan T.
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p. 8987 - 8992
(2021/07/01)
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- A case of chain propagation: α-aminoalkyl radicals as initiators for aryl radical chemistry
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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.
- Constantin, Timothée,Juliá, Fabio,Leonori, Daniele,Sheikh, Nadeem S.
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p. 12822 - 12828
(2020/12/29)
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- A hydrophilic heterogeneous cobalt catalyst for fluoride-free Hiyama, Suzuki, Heck and Hirao cross-coupling reactions in water
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A hydrophilic heterogeneous cobalt catalyst of chitosan, denoted as mTEG-CS-Co-Schiff-base, has been successfully prepared. This newly synthesized catalyst was characterized by different methods such as XRD, FE-SEM, TEM, TGA, FT-IR, 13C{1H} CP/MAS NMR, XPS and ICP analyses. The catalyst displayed excellent activity for the palladium and fluoride-free Hiyama, Suzuki, Heck and Hirao reactions of various aryl iodides, bromides and chlorides (i.e., the most challenging aryl halides which are cheaper and more widely available than aryl iodides and bromides) in water. The presence of triethylene glycol tags with hydrophilic character on the Co-complex supported on chitosan provides dispersion of the catalyst particles in water, which leads to higher catalytic performance and also facile catalyst recovery by successive extraction. It was reused for at least six successive runs without any discernible decrease in its catalytic activity or any remarkable changes in catalyst structure. The use of water as a green solvent, without requiring any additive or organic solvent, as well as use of a low cost and abundant cobalt catalyst instead of expensive Pd catalysts along with the catalyst recovery and scalability, make this method favorable from environmental and economic points of view for the C-C and C(sp2)-P coupling reactions. Notably, this is the first report on the application of a cobalt catalyst in Hiyama reactions.
- Sobhani, Sara,Hosseini Moghadam, Hadis,Skibsted, J?rgen,Sansano, José Miguel
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p. 1353 - 1365
(2020/03/11)
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- Palladium-catalyzed solvent-free preparation of arylphosphonates Arp(O)(OAr)2 from (Aro)3p via the Michaelis-Arbuzov rearrangement
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The Pd-catalyzed Michaelis-Arbuzov rearrangement of triaryl phosphites to produce the corresponding arylphosphonates in good to excellent yields is disclosed. In comparison to the traditional methods, this new method is highly atom efficient and is general, as it can be readily extended to aryl phosphonites and phosphinites. A gram-scale reaction of (PhO)3P to PhP(O)(OPh)2 with low loading of the catalyst was also demonstrated to show its potentially practical usefulness. A plausible mechanism is proposed.
- Li, Chunya,Han, Li-Biao
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p. 3613 - 3617
(2020/11/03)
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- Nickel-Catalyzed Phosphorylation of Tosylates
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Abstract: Four new bidentate phosphine ligands have been synthesized, characterized and evaluated in Ni-catalyzed C–P coupling reaction. The readily available and inexpensive highly active sulfonate Ni(cod)2-L8 catalyzes the reaction leading to
- Li, Chun-jing
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p. 725 - 730
(2020/06/30)
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- Potent Reductants via Electron-Primed Photoredox Catalysis: Unlocking Aryl Chlorides for Radical Coupling
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We describe a new catalytic strategy to transcend the energetic limitations of visible light by electrochemically priming a photocatalyst prior to excitation. This new catalytic system is able to productively engage aryl chlorides with reduction potentials hundreds of millivolts beyond the potential of Na0 in productive radical coupling reactions. The aryl radicals produced via this strategy can be leveraged for both carbon-carbon and carbon-heteroatom bond-forming reactions. Through direct comparison, we illustrate the reactivity and selectivity advantages of this approach relative to electrolysis and photoredox catalysis.
- Chernowsky, Colleen P.,Cowper, Nicholas G. W.,Wickens, Zachary K.,Williams, Oliver P.
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supporting information
(2020/02/04)
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- Cobalt catalyzed C-P bond formation by cross-coupling of boronic acids with P(O)H compounds in presence of zinc
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In our current work, we have reported the first cobalt-catalyzed cross-coupling of arylboronic acid with alkyl/aryl phosphites under mild conditions. The reaction was carried out in the presence of zinc powder as an additive and ter-pyridine as a ligand. The use of non-precious cobalt salt makes the protocol advantageous, as it is inexpensive and more abundant than the previously used methods where precious metal salts (Pd and Pt) were used. The reaction has a wide substrate scope and the products were obtained in good yields.
- Hicks, Ian,McTague, Jonathan,Hapatsha, Tatiana,Teriak, Rania,Kaur, Parminder
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- C-P bond construction catalyzed by NiII immobilized on aminated Fe3O4@TiO2 yolk-shell NPs functionalized by (3-glycidyloxypropyl)trimethoxysilane (Fe3O4@TiO2 YS-GLYMO-UNNiII
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NiII immobilized on aminated Fe3O4@TiO2 yolk-shell NPs functionalized by (3-glycidyloxypropyl)trimethoxysilane (Fe3O4@TiO2 YS-GLYMO-UNNiII) was prepared as a stable, h
- Ghasemzadeh, Maryam Sadat,Akhlaghinia, Batool
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p. 5341 - 5356
(2019/04/05)
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- Generation of Aryl Radicals from Aryl Halides: Rongalite-Promoted Transition-Metal-Free Arylation
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A new and practical method for the generation of aryl radicals from aryl halides is reported. Rongalite as a novel precursor of super electron donors was used to initiate a series of electron-catalyzed reactions under mild conditions. These transition-metal-free radical chain reactions enable the efficient formation of C-C, C-S, and C-P bonds through homolytic aromatic substitution or SRN1 reactions. Moreover, the synthesis of antipsychotic drug Quetiapine was performed on gram scale through the described method. This protocol demonstrated its potential as a promising arylation method in organic synthesis.
- Yu, Fazhi,Mao, Runyu,Yu, Mingcheng,Gu, Xianfeng,Wang, Yonghui
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p. 9946 - 9956
(2019/09/04)
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- Catalyst-free phosphorylation of aryl halides with trialkyl phosphites through electrochemical reduction
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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.
- Wang, Shuai,Yang, Cheng,Sun, Shuo,Wang, Jianbo
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supporting information
p. 14035 - 14038
(2019/11/25)
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- Electrochemical phosphorylation of arenes catalyzed by cobalt under oxidative and reductive conditions
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Catalyst capable to operate in cathode and anode spaces simultaneously was found. Electrochemical regeneration of active form of catalyst Co2+bpy (1%) under oxidative as well as reductive conditions allows the C–H/P–H coupling of dialkyl-H-phos
- Strekalova,Grinenko,Gryaznova,Kononov,Dolengovski,Budnikova
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p. 506 - 509
(2019/01/08)
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- Photoinduced Transition-Metal-Free Cross-Coupling of Aryl Halides with H-Phosphonates
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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.
- Zeng, Huiying,Dou, Qian,Li, Chao-Jun
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supporting information
p. 1301 - 1305
(2019/02/19)
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- Nickel-Catalyzed Electrochemical Phosphorylation of Aryl Bromides
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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.
- Bai, Ya,Liu, Nian,Wang, Shutao,Wang, Siyu,Ning, Shulin,Shi, Lingling,Cui, Lili,Zhang, Zhuoqi,Xiang, Jinbao
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supporting information
p. 6835 - 6838
(2019/09/30)
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- Decarbonylative Phosphorylation of Carboxylic Acids via Redox-Neutral Palladium Catalysis
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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.
- Liu, Chengwei,Ji, Chong-Lei,Zhou, Tongliang,Hong, Xin,Szostak, Michal
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supporting information
p. 9256 - 9261
(2019/11/19)
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- Synthesis of phosphonates from phenylphosphonic acid and its monoesters
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Possibilities for the mono- and diesterification of phenylphosphonic acid were evaluated considering the microwave(MW)-assisted direct esterification, and the alkylating esterification. It was found that regarding the monoesterification, the reaction with 15-fold alcohol excess in the presence of [bmim][BF4] additive utilizing MWs is superior than the approach by alkylation. At the same time, for the conversion of the monoester intermediate to the diester, the reaction with alkyl halides in the presence of triethylamine as the base, again under MW irradiation, was found to be the method of choice. Phosphonates with both identical and different alkoxy groups were made available.
- Henyecz, Réka,Kiss, Adrienn,Mórocz, Virág,Kiss, Nóra Zsuzsa,Keglevich, Gy?rgy
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supporting information
p. 2642 - 2650
(2019/08/08)
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- Arylphosphate compound and preparation method thereof
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The invention discloses an arylphosphate compound and a preparation method thereof. The preparation method includes, with arylamine and phosphite ester as reactants and tert-butyl nitrite as an accelerator, performing stirring reaction at the temperature within 70-80 DEG C for 40-60 minutes, and separating through the column chromatography to obtain a product, namely arylphosphate compound. The preparation method is a new way of synthetizing arylphosphate target compound from low-price feasible raw materials of arylamine and phosphite ester on the acid-free and metal-free condition, has the advantages of mild reaction condition, operational simplicity and the like and overcomes the big trouble to production of medical intermediates caused by residues of metal catalysts, after-treatment ofacids in medicine synthesis, and accordingly, the simple and efficient meta-free and acid-free catalysis system has great potential application value and economic benefit.
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Paragraph 0011; 0014
(2019/04/17)
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- Cu2O/TiO2 nanoparticles as visible light photocatalysts concerning C(sp2)-P bond formation
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A novel and efficient method has been developed for the construction of an aromatic-phosphorus (Ar-P) bond under visible light irradiation using Cu2O/TiO2 nanoparticles as inexpensive and available photocatalysts. This protocol is a simple system without the use of any base, ligand, oxidant, or special conditions. This is the first report for the synthesis of arylphosphonates from arylhydrazines in visible light irradiation.
- Hosseini-Sarvari, Mona,Jafari, Fattaneh,Mohajeri, Afshan,Hassani, Nasim
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p. 4044 - 4051
(2018/08/24)
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- Aryl phosphate esters compound and preparation method thereof
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The invention discloses an aryl phosphate esters compound and a preparation method thereof, wherein an organic dye is used as a photosensitizer, a catalytic amount of alkali is added, aryl hydrazine and phosphate are used as reactants, acetonitrile is used as a solvent, the temperature is controlled between 25-45 DEG C, the reaction is carried out under the irradiation of visible light for 1-6h, and the product aryl phosphate compound is separated by column chromatography. The invention provides a new method for synthesizing aryl phosphate class target compound with cheap and easily availablearyl hydrazine and phosphate ester compound as starting material for the first time. The preparation method has the advantages of mild reaction conditions, simple operation and the like; in the drug synthesis, the residual of the metal catalyst brings great trouble to the production and application of the drug, so that the metal-free catalytic system in the method has great potential application value.
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Paragraph 0022-0025
(2018/10/11)
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- Avisible-light-promoted metal-free strategy towards arylphosphonates: Organic-dye-catalyzed phosphorylation of arylhydrazines with trialkylphosphites
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A visible-light-induced metal-free catalytic system was developed for the synthesis of arylphosphonates starting from arylhydrazines and trialkylphosphites. By using the inexpensive eosin B as catalyst, sub-stoichiometric amounts of DABCO, and ambient air as oxidant, diverse arylphosphonates were obtained under visible-light irradiation. Notably, this catalytic system is suitable for gram-scale reaction by utilizing sunlight as an illumination source.
- Li, Rui,Chen, Xiaolan,Wei, Shengkai,Sun, Kai,Fan, Lulu,Liu, Yan,Qu, Lingbo,Zhao, Yufen,Yu, Bing
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supporting information
p. 4807 - 4813
(2018/12/11)
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- Visible-Light-Mediated Metal-Free Synthesis of Aryl Phosphonates: Synthetic and Mechanistic Investigations
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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.
- Lecroq, William,Bazille, Pierre,Morlet-Savary, Fabrice,Breugst, Martin,Lalevée, Jacques,Gaumont, Annie-Claude,Lakhdar, Sami
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supporting information
p. 4164 - 4167
(2018/07/29)
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- SUPPORTED MOLYBDENUM PEROXO COMPLEXES FOR TRANSFORMING ORGANO PHOSPHATE NEUROTOXINS TO A VALUE-ADDED, COMMODITY PHOSPHORUS CHEMICAL
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The invention relates to degradation of organophosphate neurotoxins with molybdenum complexes. In particular, the degradation of phosphate ester neurotoxins can be performed with molybdenum peroxo complexes resulting in recoverable phosphorus-containing compounds.
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Paragraph 0024
(2018/10/21)
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- Chemoselective Activation of Diethyl Phosphonates: Modular Synthesis of Biologically Relevant Phosphonylated Scaffolds
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Phosphonates have garnered considerable attention for years owing to both their singular biological properties and their synthetic potential. State-of-the-art methods for the preparation of mixed phosphonates, phosphonamidates, phosphonothioates, and phos
- Adler, Pauline,Pons, Amandine,Li, Jing,Heider, J?rg,Brutiu, Bogdan R.,Maulide, Nuno
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supporting information
p. 13330 - 13334
(2018/09/25)
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- P-arylation of aryl halides by an environmentally compatible method
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In this paper, palladium-DABCO complex supported on magnetic nanoparticles was successfully used as a new magnetically recoverable heterogeneous catalyst for the synthesis of arylphosphonates via P-arylation of different types of aryl halides (aryl iodides/bromides/chlorides and benzene boronic acid/sulfonate), with phosphite esters (triethyl/triphenyl/tri-iso-propyl/diethyl/diphenyl/di-iso-propyl phosphite) in neat water without using any additive. The heterogeneous catalyst was easily isolated from the reaction mixture by an external magnet and reused five times without significant degradation in its activity.
- Sobhani, Sara,Vahidi, Zahra
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p. 1280 - 1284
(2017/11/27)
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- Novel approach to metal-induced oxidative phosphorylation of aromatic compounds
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We propose a new approach to the phosphorylation of benzenes bearing both electron withdrawing and electron donating substituents on the ring and some coumarins (coumarin, 6-methylcoumarin, 7-methylcoumarin) under the action of dialkyl H-phosphonate (RO)
- Khrizanforov,Strekalova,Kholin,Khrizanforova,Kadirov,Gryaznova,Budnikova
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p. 133 - 141
(2016/11/03)
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- The Palladium Acetate-Catalyzed Microwave-Assisted Hirao Reaction without an Added Phosphorus Ligand as a “Green” Protocol: A Quantum Chemical Study on the Mechanism
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It was proved by our experiments that on microwave irradiation, the mono- or bidentate phosphorus ligands generally applied in the palladium(II)-catalyzed P–C coupling reaction of aryl bromides and dialkyl phosphites or secondary phosphine oxides may be substituted by the excess of the >P(O)H reagent that exists under a tautomeric equilibrium. Taking into account that the reduction of the palladium(II) salt and the ligation of the palladium(0) so formed requires 3 equivalents of the P-species for the catalyst applied in a quantity of 5–10%, all together, 15–30% of the P-reagent is necessary beyond its stoichiometric quantity. In the coupling reaction of diphenylphosphine oxide, it was possible to apply diethyl phosphite as the reducing agent and as the P-ligand. The reactivities of the diethyl phosphite and diphenylphosphine oxide reagents were compared in a competitive reaction. The mechanism and the energetics of this new variation of the Hirao reaction of bromobenzene with Y2P(O)H reagents (Y=EtO and Ph) was explored by quantum chemical calculations. The first detailed study on simple reaction models justified our assumption that, under the conditions of the reaction, the trivalent form of the >P(O)H reagent may serve as the P-ligand in the palladium(0) catalyst, and shed light on the fine mechanism of the reaction sequence. The existence of the earlier described bis(palladium complex) {[H(OPh2P)2PdOAc]2} was refuted by high level theoretical calculations. This kind of complex may be formed only with chloride anions instead of the acetate anion. The interaction of palladium acetate and Y2P(O)H may result in only the formation of the [(HO)Y2P]2Pd complex that is the active catalyst in the Hirao reaction. The new variation of the Hirao reaction is of a more general value, and represents the greenest protocol, as there is no need for the usual P-ligands. Instead, the >P(O)H reagent should be used in an excess of up to 30%. Hence, the costs and environmental burdens may be decreased. (Figure presented.).
- Keglevich, Gy?rgy,Henyecz, Réka,Mucsi, Zoltán,Kiss, Nóra Zs.
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p. 4322 - 4331
(2017/12/26)
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- Decarbonylative Phosphorylation of Amides by Palladium and Nickel Catalysis: The Hirao Cross-Coupling of Amide Derivatives
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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.
- Liu, Chengwei,Szostak, Michal
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supporting information
p. 12718 - 12722
(2017/10/06)
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- A palladium-catalyzed oxidative cross-coupling reaction between aryl pinacol boronates and H-phosphonates in ethanol
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The first successful oxidative coupling reaction of aryl pinacol boronic esters with H-phosphonates to deliver aryl phosphorous compounds is reported herein. These reactions between aryl boronic reagents and H-phosphonates were carried out synergistically using a Pd catalyst, additive and oxidant. Without using bases and ligands, phosphorylation was accomplished in an environmentally-friendly manner under mild conditions in ethanol.
- Chen, Te-Hsuan,Reddy, Daggula Mallikarjuna,Lee, Chin-Fa
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p. 30214 - 30220
(2017/07/07)
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- Ar-P bond construction by the Pd-catalyzed oxidative cross-coupling of arylsilanes with H-phosphonates via C-Si bond cleavage
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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.
- Luo, Haiqing,Liu, Haidong,Chen, Xingwei,Wang, Keke,Luo, Xuzhong,Wang, Kejun
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supporting information
p. 956 - 958
(2017/01/17)
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- Lanthanide Ions Coupled with Photoinduced Electron Transfer Generate Strong Reduction Potentials from Visible Light
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Metal ions can have beneficial effects on photoinduced electron transfer. Merging such metal-ion-coupled electron transfer (MCET) with consecutive photoinduced electron transfer (conPET) enables the one-electron reduction of chlorobenzene with blue light in the presence of diisopropylethylamine as an electron donor. The presence of the metal ions extends the substrate scope of the photoredox catalysis to extreme reduction potentials (beyond ?3 V vs. SCE).
- Meyer, Andreas Uwe,Slanina, Tomá?,Heckel, Alexander,K?nig, Burkhard
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supporting information
p. 7900 - 7904
(2017/06/19)
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- Synthesis method of glufosinate ammonium intermediate alkyl phosphodiester compound
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The invention discloses a synthesis method of a glufosinate ammonium intermediate alkyl phosphodiester compound. According to the method, phosphite trimester and halogenated hydrocarbon or alcohol or phenol are subjected to substitution reaction so as to obtain the glufosinate ammonium intermediate alkyl phosphodiester. The method takes phosphite trimester as the raw material to carry out substitution reaction with halogenated hydrocarbon or alcohol or phenol at certain temperature to obtain the corresponding product alkyl phosphodiester, and the product can be further prepared into glufosinate ammonium. The method changes the existing process of using methyl diethyl phosphite to prepare glufosinate ammonium, has the characteristics of low production cost, safety and environmental protection, and at the same time avoids the risk in the process of industrialization.
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Paragraph 0035; 0036
(2017/04/18)
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- Synthesis of arylphosphonates catalyzed by Pd-imino-Py-γ-Fe2O3 as a new magnetically recyclable heterogeneous catalyst in pure water without requiring any additive
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A palladium-Schiff base complex immobilized covalently on γ-Fe2O3 (Pd-imino-Py-γ-Fe2O3) was synthesized and characterized by different methods such as XRD (X-ray diffraction), SEM (scanning electron microscopy), TEM (transmission electron microscopy), FT-IR (Fourier transform infrared spectroscopy), TGA (thermogravimetric analysis), ICP (inductively coupled plasma), XPS (X-ray photoelectron spectroscopy), VSM (vibrating sample magnetometer) and elemental analysis. It was used as a new magnetically recyclable heterogeneous Pd catalyst for the synthesis of arylphosphinates via Csp2-P coupling reactions. A wide range of electrophilic benzenes were coupled successfully with triethylphosphite to generate the corresponding products in good to high yields in pure water without using any additive. The true heterogeneous Pd-imino-Py-γ-Fe2O3 could be reused simply with the aid of a magnetic bar for eight consecutive cycles without any drastic loss of its reactivity.
- Sobhani, Sara,Ramezani, Zohreh
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p. 29237 - 29244
(2018/06/06)
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- A new magnetically recoverable heterogeneous palladium catalyst for phosphonation reactions in aqueous micellar solution
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A new heterogeneous palladium complex of 2-aminothiophenol supported on nanomagnetic γ-Fe2O3 was synthesized and characterized using various methods. The catalyst was used as a magnetically recoverable heterogeneous palladium catalyst for phosphonation reactions via C-P bond formation. Using this method, a wide range of electrophilic benzenes was coupled successfully with phosphite esters (triethyl/tri-isopropyl/triphenylphosphite and diethyl/di-isopropyl/diphenylphosphite) in aqueous micellar solution to generate the corresponding arylphosphonates in good to high yields. The catalyst was separated using an external magnet and reused for six consecutive cycles without any significant loss of its reactivity.
- Sobhani, Sara,Zeraatkar, Zohre
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- The Cu-catalyzed C-P coupling of phosphonate esters with arylboronic acids
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Copper-catalyzed C-P cross coupling of phosphonate esters with arylboronic acids has been developed. The reaction provided an efficient method for aryl phosphonates under mild conditions.
- Wan,Zhao,Wang,Zhang,Li
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p. 150 - 153
(2016/03/12)
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- Preparation of organophosphorus compounds from P-H compounds using o-(trimethylsilyl)aryl triflates as aryne precursors
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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.
- Yang, Guoqiang,Shen, Chaoren,Quan, Mao,Zhang, Wanbin
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supporting information
p. 333 - 337
(2015/12/30)
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