- Toward the Efficient Synthesis of New Phosphopantothenate Derivatives by Using Chlorophosphate Reagents
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Seven new masked analogues of phosphopantothenate, suitable for an evaluation of their potential ability to restore intracellular coenzyme A (CoA) levels, were successfully synthesized in good to moderate yields. The preparation of derivatives masked with (acyloxy)alkyl groups was studied particularly in terms of synthetic efficiency, and the possibility of applying different chlorophosphate reagents for the preparation of a variety of masked derivatives was also investigated. Using this methodology, we have successfully synthesized a new chlorophosphate reagent, suitable for the introduction of the (isobutyryloxy)methyl functionality into the prodrug. Additionally, special attention was given to finding mild and economical reaction conditions for phosphorylation of biological molecules.
- Pahor, Jerca,Stavber, Stojan,?usak, Alen,Kosec, Gregor,Petkovi?, Hrvoje,Berke, Ajda Podgor?ek
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- Palladium/Xiao-Phos-Catalyzed Kinetic Resolution of sec-Phosphine Oxides by P-Benzylation
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P-stereogenic tert- and sec-phosphines have wide applications in asymmetric catalysis, materials, and pharmaceutical chemistry, however, their practical synthesis still constitutes a significant challenge. Herein, a successful kinetic resolution of rac-se
- Dai, Qiang,Liu, Lu,Zhang, Junliang
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supporting information
p. 27247 - 27252
(2021/11/17)
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- 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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- Selective Conversion of Benzylic Phosphates into Diarylmethanes Through Al(OTf)3-Catalyzed Friedel–Crafts-Type Benzylation
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Al(OTf)3 was identified as a high-performance catalyst for Friedel–Crafts-type benzylation using benzylic phosphates as electrophiles. The reaction proceeded even with 0.2 mol-% of the catalyst. A series of diarylmethanes (21 examples) was obtained in moderate to high yield. The catalyst showed unique chemoselectivity, preferentially converting the benzylic phosphate motif, even with a benzylic acetate group existed in the same molecule.
- Yurino, Taiga,Hachiya, Asuka,Suzuki, Keisuke,Ohkuma, Takeshi
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p. 2225 - 2232
(2020/04/16)
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- O-Phosphination of Aldehydes/Ketones toward Phosphoric Esters: Experimental and Mechanistic Studies
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Addition of P-H species to carbonyl groups, namely the Pudovik reaction, normally delivers hydroxyl phosphorus compounds, along with phosphate byproducts in some cases. A few controllable systems starting from phosphites were set up to mainly provide the phosphates. Herein, we present a highly selective protocol starting from phosphonate precursors leading to phosphinate derivatives. Enantioenriched phosphinates were successfully achieved from chiral phosphine oxide precursors. Experimental and theoretical investigations were conducted to understand the mechanistic details.
- Qian, Yanyan,Dai, Qiang,Li, Zhiming,Liu, Yu,Zhang, Junliang
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supporting information
p. 4742 - 4748
(2020/06/29)
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- Cetyltrimethyl ammonium bromide catalysed oxidative cross dehydrogenative coupling of benzylic C(sp3)-H bonds in methylarenes with P(O)-OH compounds
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An efficient metal-free method for the synthesis of organophosphorus compounds via oxidative cross dehydrogenative coupling of benzylic C(sp3)-H bonds in methylarenes with P(O)-OH compounds catalysed by cetyltrimethyl ammonium bromide (CTAB) is
- Li, Hang,Lei, Jian,Liu, Yongping,Chen, Yi,Au, Chak-Tong,Yin, Shuang-Feng
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p. 302 - 308
(2019/01/10)
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- BuLi-triggered phospha-Brook rearrangement: Efficient synthesis of organophosphates from ketones and aldehydes
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A variety of organophosphates are synthesized from n-BuLi-triggered, (additional) solvent-free reactions of diethyl phosphite with both activated/unactivated ketones and aldehydes preferably at room temperature via phospha-Brook rearrangement. We could successfully synthesize the naphthylic/allylic phosphates using this approach.
- Pallikonda, Gangaram,Santosh, Ranga,Ghosal, Subhas,Chakravarty, Manab
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p. 3796 - 3798
(2015/06/08)
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- Synthesis of diarylmethanes through palladium-catalyzed coupling of benzylic phosphates with arylsilanes
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An efficient approach to the benzylation of arenes has been developed. The reactions described provide straightforward access to diarylmethanes through Pd-catalyzed coupling of benzylic phosphates with arylsilanes in good to excellent yields. The reaction tolerates a wide range of functionalities such as halide, alkoxyl, and nitro groups.
- Zhang, Pengbo,Xu, Jian,Gao, Yuzhen,Li, Xueqin,Tang, Guo,Zhao, Yufen
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p. 2928 - 2932
(2015/01/16)
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- Tetrabutylammonium iodide-catalyzed phosphorylation of benzyl c-h bonds via a cross-dehydrogenative coupling (cdc) reaction
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Phosphate esters play important roles as biological active principles and synthons in chemistry. An efficient metal-free approach for the synthesis of phosphate esters through sp3 C-H activation is described. By using tetrabutylammonium iodide (Bu4NI) as a catalyst and tert-butyl hydroperoxide (TBHP) as an oxidant, various toluene derivatives and phosphorus nucleophiles are tolerated in this transformation, affording the corresponding products in moderate to good yields.
- Xu, Jian,Zhang, Pengbo,Li, Xueqin,Gao, Yuzhen,Wu, Ju,Tang, Guo,Zhaoa, Yufen
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p. 3331 - 3335
(2015/01/16)
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- Cross-hetero-dehydrogenative coupling reaction of phosphites: A catalytic metal-free phosphorylation of amines and alcohols
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Phosphorylation of amines, alcohols, and sulfoximines are accomplished using molecular iodine as a catalyst and H2O2 as the sole oxidant under mild reaction conditions. This method provides an easy route for synthesizing a variety of phosphoramidates, phosphorus triesters and sulfoximine-derived phosphoramidates which are of biological importance.
- Dhineshkumar, Jayaraman,Prabhu, Kandikere Ramaiah
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supporting information
p. 6062 - 6065
(2014/01/06)
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- β-aryl nitrile construction via palladium-catalyzed decarboxylative benzylation of α-cyano aliphatic carboxylate salts
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The palladium-catalyzed decarboxylative benzylation of α-cyano aliphatic carboxylate salts with benzyl electrophiles was discovered. This reaction exhibits good functional group compatibility and proceeds under relatively mild conditions. A diverse range of quaternary, tertiary and secondary β-aryl nitriles can be conveniently prepared by this method. Copyright
- Shang, Rui,Huang, Zheng,Xiao, Xiao,Lu, Xi,Fu, Yao,Liu, Lei
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supporting information
p. 2465 - 2472,8
(2020/08/31)
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- An efficient method for phosphorylation of alcohols: Preparation of porphyrin-derived phosphates
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An effective method for the phosphorylation of phenols and various alcohols including porphyrins bearing hydroxyl groups was developed. The reaction of 6,7-bis(3-hydroxypropyl)-1,3,5,8-tetramethyl-2,4-divinylporphyrin with dialkyl chlorophosphate in the presence of DABCO as both a catalyst and a proton scavenger gave the desired phosphate in 97% yield.
- Pisarek, Sabina,Bednarski, Hubert,Gryko, Dorota
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p. 2667 - 2671,5
(2012/12/12)
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- An efficient method for phosphorylation of alcohols: Preparation of porphyrin-derived phosphates
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An effective method for the phosphorylation of phenols and various alcohols including porphyrins bearing hydroxyl groups was developed. The reaction of 6,7-bis(3-hydroxypropyl)-1,3,5,8-tetramethyl-2,4-divinylporphyrin with dialkyl chlorophosphate in the presence of DABCO as both a catalyst and a proton scavenger gave the desired phosphate in 97% yield. Georg Thieme Verlag KG Stuttgart · New York.
- Pisarek, Sabina,Bednarski, Hubert,Gryko, Dorota
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p. 2667 - 2671
(2013/01/15)
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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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- Synthesis of functionalized diarylmethanes via a copper-catalyzed cross-coupling of arylmagnesium reagents with benzylic phosphates
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A combination of copper chloride, triethyl phosphite, and tetrabutylammonium iodide is a very efficient catalytic system for the synthesis of polyfunctionalized diarylmethanes, using the cross-coupling reaction of arylmagnesium halides with benzylic phosphates. The antibiotic Trimethoprim has been prepared using this Cu(I)-catalyzed cross-coupling in 52% overall yield (four steps).
- Kofink, Christiane C.,Knochel, Paul
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p. 4121 - 4124
(2007/10/03)
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- Suzuki-Miyaura cross-coupling of benzylic phosphates with arylboronic acids
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(Chemical Equation Presented) Suzuki-Miyaura cross-coupling of benzylic phosphates with arylboronic acids was investigated. Optimum conditions employed the simple catalytic system of palladium(II) acetate (1 mol %) and triphenylphosphine (4 mol %) with either potassium phosphate or potassium carbonate as the base and toluene as the solvent at 90°C. Using the developed conditions, a series of structurally diverse diarylmethanes were prepared.
- McLaughlin, Mark
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p. 4875 - 4878
(2007/10/03)
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- Phosphorylation of alcohols with N-phosphoryl oxazolidinones employing copper(II) triflate catalysis
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(Chemical Equation Presented) Phosphoryl transfer from N-phosphoryl 5,5-diphenyl oxazolidinone is efficiently catalyzed by copper(II) triflate. The utility of this method has been demonstrated in the phosphorylation of representative primary, secondary, tertiary, phenolic, and allylic alcohols. These reaction conditions are significantly milder than employing alkoxides and allow the phosphorylation of biologically relevant molecules.
- Jones, Simon,Smanmoo, Chaiwat
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p. 3271 - 3274
(2007/10/03)
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- N-Phosphoryl oxazolidinones as effective phosphorylating agents
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A number of N-phosphoryl oxazolidinones have been prepared and evaluated, the best being 5,5-diphenyl oxazolidinones, the utility of which was demonstrated in the phosphorylation of a number of representative primary, secondary, tertiary, and phenolic alcohols.
- Jones, Simon,Smanmoo, Chaiwat
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p. 1585 - 1588
(2007/10/03)
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- A simple, general and improved procedure for phosphorylation of alcohols catalyzed by indium(III) chloride
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A general and efficient procedure has been developed for the preparation of dialkyl phosphate esters by indium(III) chloride catalyzed phosphoryl transfer from diethyl and diphenyl chlorophosphate to a variety of alcohols and phenols in THF in presence of triethylamine.
- Ranu, Brindaban C.,Das, Arijit
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p. 1063 - 1064
(2007/10/03)
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- Enantioselective Deprotonation of Benzyl Phosphates by Homochiral Lithium Amide Bases - Configurational Stability of Benzyl Carbanions with a Dialkoxyphosphoryloxy Substituent and Their Rearrangement to Optically Active α-Hydroxy Phosphonates
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Benzyl dialkyl phosphates are deprotonated enantioselectively by homochiral lithium amides of isopropyl(1-phenylethyl)amine or bis(1-phenylethyl)amine.The short-lived benzylic carbanions formed are virtually configurationally stable relative to the rearrangement to optically active phenylhydroxymethylphosphonates.The enantiomeric excesses are up to 50percent.The pro-(S) hydrogen is removed by amides having (S) configuration.Homochiral diethyl (S)-phenylmethyl phosphate is deprotonated by both LDA and n-BuLi with a high primary kinetic isotope effect (kH/D ca. 50) and isomerizes to the corresponding α-hydroxy phosphonate with an enantiomeric excess of up to 85percent. - Keywords: Phosphate-phosphonate rearrangement / Carbanions, benzylic, configurational stability of / Phosphonates / Lithium amides, homochiral
- Hammerschmidt, Friedrich,Hanninger, Achim
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p. 823 - 830
(2007/10/02)
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- Direct Transformation of Trialkyl Phosphates into Organolithium Compounds by a DTBB-Catalysed Lithiation
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The reaction of different alkylic or phenylic phosphates 1 with an excess of lithium powder and a catalytic amount of DTBB (5 mol percent) in the presence of an electrophile -Barbier-type reaction conditions- in THF at -30 deg C leads to the formation of the expected products 2, resulting from the reaction of the in situ generated organolithium compound with the corresponding electrophile.
- Guijarro, David,Mancheno, Balbino,Yus, Miguel
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p. 8551 - 8558
(2007/10/02)
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- Photochemistry of phosphate esters: An efficient method for the generation of electrophiles
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The photochemical cleavage of benzyl diethyl phosphates, 1a-g, has been examined in tert-butyl alcohol, which produces the corresponding benzyl tert-butyl ether as the major solvolysis product upon direct irradiation. The multiplicity of the reactive excited state has been established as the singlet state. Evidence favoring an intermediate benzyl cation-phosphate ion pair formed from photofragmentation includes oxygen-18 scrambling, racemization of chiral benzyl phosphates, and substituent effects on the rate of reaction. The existence of an electrophilic intermediate is further supported by a linear free energy relationship for the rate of disappearance of 1, kdis, with Hammett σ, which gave a ρ value of -0.90 and for the rate of appearance of 2, kapp, a Hammett ρ value of -0.97. Possible mechanisms including an electron transfer either before or after homolysis or simple heterolysis of the ester bond are evaluated.
- Givens, Richard S.,Matuszewski, Bogdan,Athey, Phillip S.,Robert Stoner
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p. 6016 - 6021
(2007/10/02)
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- A New Phosphorylation Method via O-Diethylboryl Intermediates
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Diphenylchlorophosphine and diethylchlorophosphite react with acetylacetone to generate intermediate phosphine enolates 3 which are quenched with O-diethylboryl derivatives and then oxidized with hydrogen peroxide to give diphenylphosphinates 4 and diethylphosphates 5. - Keywords: Phosphorylation, Diphenylphosphinates, Diethylphosphates, O-Diethylboryl Intermediates
- Dahlhoff, Wilhelm V.,Taba, Kalulu M.
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p. 1260 - 1262
(2007/10/02)
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- The Selective Dealkylation of Mixed Esters of Phosphoric Acid and Phenylphosphonic Acid Using Cation Exchange Resin
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Cation exchange resin (SO3H) is a highly selective dealkylation reagent for mixed esters of phosphorus oxyacids bearing primary and secondary alkyl groups.The desired products which were produced by dealkylation of the secondary alkyl group were obtained in high yields under anhydrous and mild conditions.Keywords - dealkylation; cation exchange resin; carbonium ion; phosphorus oxyacid ester; trialkyl phosphate; dialkyl phenylphosphonate; p-toluenesulfonic acid
- Nitta, Yoshihiro,Arakawa, Yasushi
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p. 3121 - 3129
(2007/10/02)
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- REACTIONS EN MILIEU HETEROGENE LIQUIDE-SOLIDE: REACTIONS DE WITTIG-HORNER ET ADDITION DU PHOSPHITE DE DIETHYLE SUR LES COMPOSES CARBONYLES EN PRESENCE DE KF, 2H2O.
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Potassium fluoride dihydrate in solid-liquid two phase systems, eventually with phase transfer catalysis, is a moderate base which can be used for Wittig-Horner reaction and synthesis of hydroxyphosphonates.
- Texier-Boullet, F.,Foucaud, A.
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p. 2161 - 2164
(2007/10/02)
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