- Mechanistic insight into the nickel-catalyzed cross-coupling of aryl phosphates with arylboronic acids: Potassium phosphate is not a spectator base but is involved in the transmetalation step in the Suzuki-Miyaura reaction
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Spectator or actor? Density functional theory calculations were performed to examine the role of the base in the nickel-catalyzed cross-coupling of aryl phosphates with arylboronic acids. Potassium phosphate was found to not act as a spectator base but was involved in the transmetalation step, as shown by a lower barrier than that of a base-free process, owing to the activation of the carbon-boron bond by the base. Further experimental observations support the theoretical findings. Copyright
- Liu, Liu Leo,Zhang, Shuangyan,Chen, Hu,Lv, Ye,Zhu, Jun,Zhao, Yufen
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Read Online
- A convenient method for the phosphorylation of phenols with diethyl cyanophosphonate
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Phosphorylation of phenols with diethyl cyanophosphonate in methylene chloride solution at 0°C is an easy, rapid and good yielding reaction.
- Guzman, Angel,Diaz, Eduardo
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Read Online
- Electrochemical phosphorylation of arenols and anilines leading to organophosphates and phosphoramidates
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A practical phosphorylation for generating organophosphates and phosphoramidatesviaelectrochemical dehydrogenative cross-coupling of P(O)H compounds with arenols and anilines is disclosed. This method involves using inorganic iodide salts as both redox catalysts and electrolytes in an undivided cell without the addition of oxidants or bases. A preliminary mechanistic study suggests that radicals are not involved in this process. This method is green and eco-friendly and has good functional group tolerance, high yields and broad substrate scope, with the potential for practical synthesis.
- Xu, Pan,Zhong, Zijian,Zhou, Aihua
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supporting information
p. 5342 - 5347
(2021/06/30)
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- LiI/TBHP Mediated Oxidative Cross-Coupling of P(O)–H Compounds with Phenols and Various Nucleophiles: Direct Access to the Synthesis of Organophosphates
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An efficient and mild method for the direct phosphorylation of phenols, alcohols, and amines with P(O)–H has been reported by LiI/TBHP mediated oxidative cross-coupling reaction. Moreover, this protocol extended to β-keto esters for the synthesis of enol phosphates using H-phosphonates. Notably, this developed method applied for the synthesis of organopesticides such as paraoxon, cyanophos, and methyl parathion. The key features of this protocol are mild conditions, short reaction time, good functional group tolerance, and broad substrate scope.
- Anitha, Thippani,Ashalu, Kashamalla Chinna,Sandeep, Mummadi,Mohd, Aabid,Wencel-Delord, Joanna,Colobert, Francoise,Reddy, Kallu Rajender
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p. 7463 - 7474
(2019/12/03)
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- Tf2O-Promoted Activating Strategy of Phosphate Analogues: Synthesis of Mixed Phosphates and Phosphinate
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A metal-, toxic chloride reagent-free activating strategy of various phosphates has been developed. This method enables the facile synthesis of functional phosphates such as alkyl phosphates, aza phosphates, thiophosphate, and mixed diaryl phosphates. A transient phosphorylpyridin-1-ium species in situ generated from phosphates with Tf2O/pyridine readily undergoes a substitution reaction with diverse nucleophiles to form versatile phosphate compounds.
- Huang, Hai,Ash, Jeffrey,Kang, Jun Yong
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supporting information
p. 4938 - 4941
(2018/08/24)
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- Synthesis, biochemical evaluation, and molecular modeling studies of aryl and arylalkyl di-n-butyl phosphates, effective butyrylcholinesterase inhibitors
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A series of dialkyl aryl phosphates and dialkyl arylalkyl phosphates were synthesized. Their inhibitory activities were evaluated against acetylcholinesterase (AChE) and butyrylcholinesterase (BChE). The di-n-butyl phosphate series consistently displayed selective inhibition of BChE over AChE. The most potent inhibitors of butyrylcholinesterase were di-n-butyl-3,5-dimethylphenyl phosphate (4b) [KI?=?1.0?±?0.4?μM] and di-n-butyl 2-naphthyl phosphate (5b) [KI?=?1.9?±?0.4?μM]. Molecular modeling was used to uncover three subsites within the active site gorge that accommodate the three substituents attached to the phosphate group. Phosphates 4b and 5b were found to bind to these three subsites in analogous fashion with the aromatic groups in both analogs being accommodated by the “lower region,” while the lone pairs on the P[dbnd]O oxygen atoms were oriented towards the oxyanion hole. In contrast, di-n-butyl-3,4-dimethylphenyl phosphate (4a) [KI?=?9?±?1?μM], an isomer of 4b, was found to orient its aromatic group in the “upper left region” subsite as placement of this group in the “lower region” resulted in significant steric hindrance by a ridge-like region in this subsite. Future studies will be designed to exploit these features in an effort to develop inhibitors of higher inhibitory strength against butyrylcholinesterase.
- Nakayama, Kensaku,Schwans, Jason P.,Sorin, Eric J.,Tran, Trina,Gonzalez, Jeannette,Arteaga, Elvis,McCoy, Sean,Alvarado, Walter
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p. 3171 - 3181
(2017/05/29)
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- New benzotriazole-based reagents for the phosphonylation of various N-, O-, and S-nucleophiles
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Benzotriazole surrogates showing higher stabilities than the corresponding chlorophosphates, allow phosphonylation of a variety of N-, O-, and S-nucleophiles in good yields.
- Panmand, Deepak S.,Tiwari, Anand D.,Panda, Siva S.,Monbaliu, Jean-Christophe M.,Beagle, Lucas K.,Asiri, Abdullah M.,Stevens, Christian V.,Steel, Peter J.,Hall, C. Dennis,Katritzky, Alan R.
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supporting information
p. 5898 - 5901
(2015/01/08)
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- Triethylphosphate/phosphorus pentoxide as an efficient reagent for the phosphorylation of phenols
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A simple, efficient, and novel method has been developed for the phosphorylation of phenols. Treatment of phenols with a mixture of triethylphosphate/phosphorus pentoxide gives the corresponding phosphate derivatives in good yields. This method is easy, rapid, and offers good yields for the phosphorylation of phenols. The reaction of triethylphosphate with phosphorus pentoxide was also studied by variable-temperature 31P-NMR spectroscopy. Copyright
- Kaboudin, Babak,Mostafalu, Ramin
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experimental part
p. 776 - 780
(2012/06/30)
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- Naphthoxaphospholes as examples of fluorescent phospha-acenes
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Seven new fluorescent 2-R-naphtho[2,3-d]oxaphospholes (R-NOPs) (4a-g; R = tBu (a), Ad (b), C6H5 (c), 4-MeC 6H4 (d), 4-ClC6H4 (e), 4-BrC 6H4 (f), 4-MeOC6H4 (g)), have been synthesized by cyclocondensation reactions of benzimidoyl chlorides with 3-phosphino-2-naphthol (3). The compounds were characterized by multinuclear NMR, UV-vis, and fluorescence spectroscopy. Compounds 4a-d and 4g were characterized by cyclic voltammetry experiments. The solid state structures of compounds 4b and 4d were also determined by single-crystal X-ray diffraction experiments.
- Laughlin, Feng Li,Rheingold, Arnold L.,Deligonul, Nihal,Laughlin, Brynna J.,Smith, Rhett C.,Higham, Lee J.,Protasiewicz, John D.
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supporting information
p. 12016 - 12022
(2013/03/14)
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- Nickel-catalyzed amination of aryl phosphates through cleaving aryl C-O bonds
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The amination of triaryl phosphates was achieved using a Ni(II)-(σ-Aryl) complex/NHC catalyst system in dioxane at 110 °C in the presence of NaH as base. Electron-neutral, -rich, and -deficient triaryl phosphates were coupled with a wider range of amine partners including cyclic and acyclic secondary amines, aliphatic primary amines, and anilines in good to excellent yields.
- Huang, Jin-Hua,Yang, Lian-Ming
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supporting information; experimental part
p. 3750 - 3753
(2011/09/14)
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- Phosphorylation of phenols with diethyl chlorophosphonate on the surface of magnesia
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Phosphorylation of phenols with diethyl chlorophosphonate on the surface of magnesia is an easy, rapid, safe and high-yielding reaction.
- Kaboudin
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p. 402 - 403
(2007/10/03)
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- NICKEL-CATALYZED CROSS-COUPLING OF ARYL PHOSPHATES WITH GRIGNARD AND ORGANOALUMINIUM REAGENTS. SYNTHESIS OF ALKYL-, ALKENYL-, AND ARYLBENZENES FROM PHENOLS
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Aryl phosphates derived from phenols were converted into alkyl-, alkenyl-, and aryl-benzenes in high yields by cross-coupling with various kinds of Grignard and organoaluminium reagents in the presence of nickel(II) catalysts.
- Hayashi, Tamio,Katsuro, Yoshio,Okamoto, Yasuo,Kumada, Makoto
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p. 4449 - 4452
(2007/10/02)
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