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Product Citations

Wen Ren ; Yuling Deng ; Jacob D. Ward ; Rebecca Vairin ; Ruoli Bai b ; Hashini I. Wanniarachchi , et al.

Abstract: The synthesis and evaluation of small-molecule inhibitors of tubulin polymerization remains a promising approach for the development of new therapeutic agents for cancer treatment. The natural products colchicine and combretastatin A-4 (CA4) inspired significant drug discovery campaigns targeting the colchicine site located on the beta-subunit of the tubulin heterodimer, but so far these efforts have not yielded an approved drug for cancer treatment in human patients. Interest in the colchicine site was enhanced by the discovery that a subset of colchicine site agents demonstrated dual functionality as both potent antiproliferative agents and effective vascular disrupting agents (VDAs). Our previous studies led to the discovery and development of a 2-aryl-3-aroyl-indole analogue (OXi8006) that inhibited tubulin polymerization and demonstrated low nM IC50 values against a variety of human cancer cell lines. A water-soluble phosphate prodrug salt (OXi8007), synthesized from OXi8006, displayed promising vascular disrupting activity in mouse models of cancer. To further extend structure-activity relationship correlations, a series of 6-aryl-3-aroyl-indole analogues was synthesized and evaluated for their inhibition of tubulin polymerization and cytotoxicity against human cancer cell lines. Several structurally diverse molecules in this small library were strong inhibitors of tubulin polymerization and of MCF-7 and MDA-MB-231 human breast cancer cells. One of the most promising analogues (KGP591) caused significant G2/M arrest of MDA-MB-231 cells, disrupted microtubule structure and cell morphology in MDA-MB-231 cells, and demonstrated significant inhibition of MDA-MB-231 cell migration in a wound healing (scratch) assay. A phosphate prodrug salt, KGP618, synthesized from its parent phenolic precursor, KGP591, demonstrated significant reduction in bioluminescence signal when evaluated in vivo against an orthotopic model of kidney cancer (RENCA-luc) in BALB/c mice, indicative of efficacy. The most active compounds from this series offer promise as anticancer therapeutic agents.

Keywords: Inhibitors of tubulin polymerization ; Vascular disrupting agents ; synthesis ; Molecular docking ; Antiproliferative agents ; Inhibitors of cell migration

Purchased from AmBeed: ; ; ; ; ; 64-86-8 ; ; ; ; ; ; ; ; 4521-61-3 ; 4521-61-3 ; 87199-18-6 ; 64-86-8 ; 64-86-8 ; 128796-39-4 ; 5720-05-8 ; 64-86-8

Alternative Products

Product Details of 3-Nitrophenylboronic acid

CAS No. :13331-27-6
Formula : C6H6BNO4
M.W : 166.93
SMILES Code : C1=C(C=CC=C1[N+]([O-])=O)B(O)O
MDL No. :MFCD00007193
InChI Key :ZNRGSYUVFVNSAW-UHFFFAOYSA-N
Pubchem ID :1677

Safety of 3-Nitrophenylboronic acid

GHS Pictogram:
Signal Word:Warning
Hazard Statements:H315-H319-H335
Precautionary Statements:P261-P305+P351+P338

Application In Synthesis of 3-Nitrophenylboronic acid

* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.

  • Downstream synthetic route of [ 13331-27-6 ]

[ 13331-27-6 ] Synthesis Path-Downstream   1~28

  • 1
  • [ 1206-36-6 ]
  • [ 13331-27-6 ]
  • [ 2113-58-8 ]
  • 2
  • [ 13331-27-6 ]
  • [ 108-90-7 ]
  • [ 2113-58-8 ]
YieldReaction ConditionsOperation in experiment
57% With 2Na(1+)*C26H18N2O8PdS2(2-); potassium carbonate; In water; at 100℃; for 6h; General procedure: The Suzuki reaction was performed in a 50 mL round-bottomed flask, aryl halide (0.5 mmol), arylboronic acid (0.65 mmol), K2CO3 (1 mmol), Complex 1 (0.2-1 mol%) and water (4 mL) were charged and stirred for the required time at room temperature for aryl bromides or at 100 C for aryl chlorides. After completion, the mixture was cooled down to room temperature, diluted with water (10 mL) and extracted with diethyl ether (3 × 15 mL). The organic layer was washed with brine (3 × 15 mL), dried over anhydrous Na2SO4. The crude products were chromatographed on silica gel (ethyl acetate/hexane).
57% With sodium hydrogencarbonate; In water; at 20℃; for 6h;Green chemistry; General procedure: In a representative experiment, bromobenzene (0.1mmol, 15.7mg) was dissolved in 3ml deionized water. Phenylboric acid (0.15mmol, 18.4mg) and NaHCO3 (0.15mmol, 12.6mg) were added to the mixture, and then PdatCOFs catalyst (4mg) was added. Stir vigorously at room temperature and monitor the reaction by TLC. After the reaction, the catalyst was centrifuged at high speed, washed with deionized water (3 × 3mL) and ethanol (3 × 3mL), and dried in vacuum. At the same time, the crude product was purified by rapid chromatography and the corresponding product was obtained.
53% With Pd/C; tetrabutylammomium bromide; potassium carbonate; In water; at 100℃; for 70h; General procedure: Reaction Conditions A: To a tube equipped with a magnetic stir barwere added the catalyst 1 (28 mg, 0.4 mol% Pd), TBAB (0.5 equiv),K2CO3 (138 mg, 2.0 equiv), arylboronic acid (1.5 equiv), and arylchloride (0.5 mmol) in turn. Subsequently, the solvent H2O (1.0mL) was added under air atmosphere. The reaction mixture wasthen heated to 100 C and stirred until the aryl chloride was completelyconsumed as determined by TLC. After completion of thereaction, the reaction mixture was purified by silica gel columnchromatography to afford the desired pure product
26% With C26H36Cl2N2O4Pd2; sodium carbonate; butyltrimethylammonium bis(trifluoromethylsulfonyl)azanide; at 80℃; for 12h;Catalytic behavior; General procedure: In a 25 ml round bottom flask, the catalyst (1) (0.1 mg,0.012 mol % Pd)/ catalyst (2) (0.2 mg, 0.012 mol % Pd) was dissolvedin [TMBA]NTf2 (0.5 ml). To this were added, 4-iodoanisole(0.1 g, 1 mmol), 3-chlorophenyl boronic acid (0.1 g, 1.5 mmol),and sodium carbonate (0.09 g, 2 mmol). The mixture was magneticallystirred in a pre-heated oil bath at 80 C for 12 h. The mixturewas allowed to cool, extracted with diethyl ether (5 5 ml), andthe ethereal phase was analyzed by GC-MS analysis. Further, theresidue from the concentrated ethereal phase was purified by silicagel column chromatography (hexane/ethyl acetate; 9:1) to obtainthe desired product. The catalyst and ionic liquid left after the reactionin the reaction flask were dried under vacuum and furthersubjected to a fresh dose of reactants to assess the recyclabilityof the catalyst and ionic liquid upto seven cycles.

  • 3
  • [ 1920-66-7 ]
  • [ 13331-27-6 ]
  • 4-amino-5-nitro-2-(3-nitrophenyl)pyrimidine [ No CAS ]
  • 4
  • [ 618-89-3 ]
  • [ 13331-27-6 ]
  • [ 149506-24-1 ]
YieldReaction ConditionsOperation in experiment
26% With tetrakis(triphenylphosphine) palladium(0); sodium carbonate; In water; toluene; at 20 - 80℃; for 5h;Inert atmosphere; [000408] Synthesis of methyl 3’-nitro-[l, 1’-biphenylj-3-carboxylate (515): To a stirred solution of <strong>[618-89-3]methyl 3-bromobenzoate</strong> 514 (2.5 g, 14.99 mmol) and (3-nitrophenyl) boronic acid 382 (3.8 g, 17.99 mmol) in toluene (20 mL) under inert atmosphere were added sodium carbonate (3.17 g, 29.99 mmol in 20 mL of H20) at RT and purged under argon atmosphere for 20 mm. To this was added Pd(PPh3)4 (693 mg, 0.59 mmol) and heated to 80 C for 5 h. The reaction was monitored by TLC; after completion of the reaction, the reaction mixture was diluted with EtOAc (200 mL). The organic extract was dried over sodium sulfate, filtered and concentrated in vacuo to obtain the crude. The crude was purified through silica gel column chromatography using 10% EtOAc/ hexanes to afford compound 515 (1 g, 26%) as yellow liquid. TLC: 15% EtOAc/ hexanes (R 0.5); 1H NMR (400 MHz, DMSO-d6): ö 8.48-8.46 (m, 1H), 8.30-8.25 (m, 2H), 8.22-8.18 (m, 1H), 8.11-8.07 (m, 1H), 8.04 (dt,J 7.8, 1.3 Hz, 1H),7.80 (t, J= 8.0 Hz, 1H), 7.69 (t, J= 7.8 Hz, 1H), 3.91 (s, 3H).
With palladium 10% on activated carbon; sodium carbonate; In methanol;Reflux; [0089] A mixture of (3-nitrophenyl)boronic acid and <strong>[618-89-3]methyl 3-bromobenzoate</strong> was placed into a reaction vessel with 10% palladium on carbon (Pd/C) and sodium carbonate (Na2C03) in methanol (MeOH). The reaction mixture was held at reflux until the starting materials had been converted into methyl 3'-nitro-[l1,1]-biphenyl]-3-carboxylate. The methyl 3'-nitro-[1,1]biphenyl]-3-carboxylate was maintained in the reaction vessel, used without purification, isopropyl acetate was added to the reaction vessel and the mixture subsequently reacted with 10% Pd/C in a hydrogen atmosphere to yield methyl 3'-amino-[1,1]-biphenyl]- 3-carboxylate.
  • 5
  • [ 29022-11-5 ]
  • [ 13331-27-6 ]
  • [ 210282-31-8 ]
  • 2-(2-carboxy-ethyl)-[1,3]oxazinane-3-carboxylic acid <i>tert</i>-butyl ester [ No CAS ]
  • [(5S,10bR)-8-(3-Nitro-phenyl)-3-oxo-1,2,3,5,6,10b-hexahydro-pyrrolo[2,1-a]isoquinoline-5-carbonyl]-amino}-acetic acid [ No CAS ]
  • 6
  • [ 29022-11-5 ]
  • [ 13331-27-6 ]
  • [ 210282-31-8 ]
  • 2-(2-carboxy-ethyl)-[1,3]oxazinane-3-carboxylic acid <i>tert</i>-butyl ester [ No CAS ]
  • 2-{2-[1-(carboxymethyl-carbamoyl)-2-(3'-nitro-biphenyl-3-yl)-ethylcarbamoyl]-ethyl}-[1,3]oxazinane-3-carboxylic acid <i>tert</i>-butyl ester [ No CAS ]
  • 7
  • [ 108-86-1 ]
  • [ 13331-27-6 ]
  • [ 2113-58-8 ]
YieldReaction ConditionsOperation in experiment
95% With potassium carbonate; In ethanol; water; at 80℃; for 0.75h; General procedure: General procedure: Aryl halide (1.0 mmol), arylboronic acid (1.2 mmol), base (2.5 mmol), and Fe3O4/SiO2-Met-Pd(OAc)2 (10 mg, 0.14 mol% Pd) were added to the vessel (10 mL) with 3 mL of solvent. The mixture was continuously stirred at 80 C in an air atmosphere for the desired time until complete consumption of the starting aryl halide as monitored by TLC. After magnetic separation of the catalyst, the product was extracted with diethyl ether and purified by column chromatography (n-hexane: chloroform). In the recycling experiment, the separated catalyst was then washed with ether and dried under vacuum to remove residual solvent
94% With potassium carbonate; In ethanol; water; at 80℃; for 2h; Suzuki-Miyaura coupling reaction;In a typical reaction, to a solution of 1 mmol of the aryl halide in 5 ml of water/ethanol (1:1) was added 1.1 mmol of phenyl boronic acid, 276 mg of K2CO3 (2 mmol) followed by 15 mg of the solid catalyst (1 mol%). The mixture was then stirred for the desired time at 80 C. The reaction was monitored by thin layer chromatography (TLC). After completion of reaction, the reaction mixture was cooled to room temperature and the catalyst (SBA-15/Met/Pd(II)) was recovered by centrifuge and washed with ethyl acetate and ethanol.The combined organic layer was dried over anhydrous sodium sulfate and evaporated in a rotary evaporator under reduced pressure. The crude product was purified by column chromatography.
93% With palladium diacetate; metformin hydrochloride; potassium carbonate; In ethanol; water; at 80℃; for 2h;Green chemistry; General procedure: To a 5 mL flask containing a mixture of Pd(OAc)2 (0.01 mmol, 0.025 g), Met.HCl (0.02 mmol, 0.033 mg), and K2CO3 (2 mmol, 276 mg) in distilled H2O (1.5 mL) and EtOH (99%, 1.5 ml) were added aryl halide (1 mmol) and boronic acid (1.1 mmol) at 80 C, and the mixture stirred for the appropriate amount of time (see Table 2). The progress of the reaction was monitored by TLC. After completion of the reaction, the mixture was washed with EtOAc (5Χ1ml) and the organic phase separated and evaporated. Further purification was by column chromatography (EtOAc/n-hexane) gave the desired coupled product.
93% With Pd/C; potassium carbonate; In water; N,N-dimethyl-formamide; at 110℃; for 2.5h; General procedure: To a tube equipped with a magnetic stir bar were added catalyst 1(7.0 mg, 0.1 mol% Pd), K2CO3 (138 mg, 2.0 equiv), arylboronicacid (1.1 equiv), and aryl bromide (0.5 mmol) in turn. Subsequently,the solvent (DMF-H2O, 3:2, 2.0 mL, v/v) was added under an airatmosphere. The reaction was then heated to 40 C and stirred untilthe aryl bromide was completely consumed as determined by TLC.After completion of the reaction, the reaction mixture was purifiedby silica gel column chromatography to afford the desired pureproduct.
90% With potassium carbonate; In water; at 50℃; for 3h; General procedure: In a test tube equipped with a magnetic stirrer bar, thearyl halide 1 (1 mmol) was mixed with phenyl boricacid 2 (1.2 mmol), K2CO3(2 mmol), and the Pd-catalyst(0.1mol% Pd) in 2 ml of H2Oin air. The reaction mixturewas then stirred at 50 C for appropriate time. After completionof the reaction, the catalyst was removed by magnetand washed with ethanol and water (3 × 5 ml). The aqueouslayer was extracted with chloroform, then organic layerdried over anhydrous MgSO4.The solvent was evaporatedunder reduced pressure to give the corresponding biarylcompounds. All the products were previously reported [5,8-12] and were confirmed by the spectroscopic methodusing 1H and 13C NMR (see supporting information).
87% With 0.1 % Cu/C; potassium carbonate; In water; at 50℃; for 4h;Green chemistry; General procedure: In a test tube, 1.0 mmol of aryl halides 1, 1.2 mmol of phenylboronic acid 2 were mixed together and then 2.0 mmol of K2CO3, and the Cu/Cnano-catalyst (0.1 mol % Cu) in 2 mL of H2O, were added in air. The reaction mixture was then stirred at 50 C for appropriate time. After completion of the reaction (monitored by TLC), the catalyst was removed by simple filtration. The recycled catalyst was was hed with ethanol and water (3 × 5 mL) and dried at 60 C in oven for further use. The aqueous layer was extracted with ethyl acetate, and organic layer dried over anhydrous MgSO4. The solvent was evaporated under reduced pressure to give the corresponding biaryl compounds.
71% With tetrabutylammomium bromide; potassium carbonate; In water; at 90℃; for 4h;Green chemistry; General procedure: 25-ml RB was charged with 4-iodo anisole (1.0 mmol), phenyl boronic acid (1.5 mmol), GO-PMMA-Pd catalyst (0.3 mol %), K2CO3 (1 mmol), TBAB (10 mol %) and 2 ml water. The mixture was allowed to stir at 90 C for an appropriate time (Table 1) and the extent of the reaction was monitored by thin layer chromatography (TLC). After the completion of the reaction, the reaction mixture was extracted by ethyl acetate (2×25 mL) and washed with water repeatedly. The catalyst was filtered off and washed several times with ether and water (1:1) until no significant product was obtained in the wash. The recoverd catalyst was reused for the next coupling experiment. The reaction mixture was dried over anhydrous Na2SO4, concentrated in vacuum and purified by column chromatography on silica gel 60-120 mesh using petroleum ether as eluent to obtain pure product. The catalyst recoverd after 5th run was subjected to ICP-AES for Pd content analysis. The isolated products were analysed by 1H NMR and 13C NMR spectroscopy.
53% With Pd(memantine)2Cl2; sodium hydroxide; In ethanol; at 80℃; for 24h; General procedure: In the reaction tube with a magnetic bar was added the solution of aryl bromides (0.5 mmol) and phenylboronic acid (91 mg, 0.75 mmol), NaOH (24 mg, 0.6 mmol), complex 1 (0.0001-0.02 mol%, dissolved in DMA) and ethanol (3 mL). After stirred for the required time in the preset conditions, the reaction mixture was cooled to room temperature, and then quenched by 1 mL brine and 3 mL water, and extracted with ethyl acetate (3×5 mL). The combined organic layer was dried over anhydrous MgSO4 and the filtrate was concentrated to dryness under reduced pressure. The crude products were purified by column chromatography (petroleum ether, ethyl acetate) on silica gel.
With C24H20Cl2NPPdS; potassium carbonate; palladium; In toluene; at 100℃; for 24h; General procedure: A 100 ml round bottom flask was fitted with a reflux condenser and a magnetic stirrer bar. The flask was charged with toluene (15 ml) and the appropriate amount of catalyst reagents and the internal standard (n-Decane: 2.59 mmol). The contents were thoroughly mixed and an initial sample (t0) was then taken. The reaction flask was placed in an oil bath at the desired temperature and the reaction mixture allowed to heat/reflux with stirring. A sample was taken and analyzed every 10 min for the first hour and every 30 min thereafter until t3h. In cases where conversionwas not complete after 3 h, the reaction mixturewas then allowed to stir for a total of 24 h. The reaction at 140 C was performed in a sealed tube. All catalytic reactions were done under aerobic conditions. Percentage conversions were determined by GC with n-decane as the internal standard and the coupling products were characterized by mass spectrometry (Table 4) as well as 1H NMR spectroscopy (Entry 5, Table 4 only).
With C31H33Cl2N2PPd; potassium hydroxide; In decane; N,N-dimethyl-formamide; at 150℃; for 3h;Catalytic behavior; General procedure: The Suzuki-Miyaura cross-coupling reactions were performed in acarousel using 24 × 150 mm quick-thread glass reaction tubes. Thegeneral procedure is similar to that given for the Mizoro-Heck Crosscouplingreactions, however, boronic acid is used herein instead of analkene. The GC was initially calibrated using standard samples ofboronic acid, toluene, n-decane and the aryl halide in order to accuratelydetermine the retention times of these compounds. Also, the reactionmixture in the reaction vessel was sampled to determine time zerovalues and analysed by GC to determine the ratios of the various components.The required catalyst amount (mol %) was then added and thereaction proceeded with a stirring rate of 600 rpm. Upon the elapse ofthe reaction time, the aryl halide conversion to biphenyl was calculatedby analysing the retention peak areas of the aryl halide with reference ton-decane as an internal standard. The NMR data of the isolated productsare given in the Supplementary Information (SI2).

  • 8
  • [ 591-50-4 ]
  • [ 13331-27-6 ]
  • [ 2113-58-8 ]
YieldReaction ConditionsOperation in experiment
99% With C22H24Cl2N6O2Pd2; potassium carbonate; In ethanol; water; for 4h;Reflux;Catalytic behavior; General procedure: In a 10 mL glass tube containing a Teflon-coated stir bar was placed p-bromobenzaldehyde 2e (0.05 g, 0.27 mmol, 1 equiv), phenylboronic acid 1a (0.05 g, 0.40 mmol, 1.5 equiv), 2M K2CO3 (0.33 mL, 0.67 mmol, 2.5 equiv), 4-AAP-Pd(II) (0.28 mg, 0.3 mol % Pd) and EtOH (2 mL). The mixture was stirred at reflux for 4 h. After cooling, the mixture was diluted with ether Et2O (5 mL), washed with sat. aq. NaHCO3 (3 mL), brine (3 mL) and dried over Na2SO4. Evaporation of the solvent and purification of the residue over a silica gel column (Hex: AcOEt 90:10), furnished the biphenyl 3q.
93% With potassium carbonate; In water; at 50℃; for 2.5h; General procedure: In a test tube equipped with a magnetic stirrer bar, thearyl halide 1 (1 mmol) was mixed with phenyl boricacid 2 (1.2 mmol), K2CO3(2 mmol), and the Pd-catalyst(0.1mol% Pd) in 2 ml of H2Oin air. The reaction mixturewas then stirred at 50 C for appropriate time. After completionof the reaction, the catalyst was removed by magnetand washed with ethanol and water (3 × 5 ml). The aqueouslayer was extracted with chloroform, then organic layerdried over anhydrous MgSO4.The solvent was evaporatedunder reduced pressure to give the corresponding biarylcompounds. All the products were previously reported [5,8-12] and were confirmed by the spectroscopic methodusing 1H and 13C NMR (see supporting information).
90% With sodium hydroxide; In ethanol; water; at 25℃; for 3h; General procedure: The Pd/IL-NH2/SiO2/Fe3O4 catalyst (19 mg, Pd: 0.5 mmol %), aryl halide (0.5 mmol), arylboronic acid (0.75 mmol), base (1 mmol), and solvent (3 mL) were added into a 10 mL glass test tube. Then the reaction was allowed to proceed at room temperature (25 C). After the reaction was finished as monitored by thin layer chromatography (TLC), the catalyst was magnetically separated and washed two times with ethyl acetate (1 mL). To obtain the GC yield, the combined organic phase was analyzed by a gas chromatograph (GC) equipped with a flame ionization detector (FID) using dodecane as an internal standard (Angilent 7890A, HP-5, 30 m 0.32 mm). To obtain the isolated yield, the combined organic phase was concentrated and the products were purified by column chromatography over silica gel. For reuse of the catalyst, after magnetically recovered, the catalyst was successively rinsed with ethyl acetate (1 mL 2) and water (0.5 mL), and dried at room temperature ready for the next cycle.
90% With potassium carbonate; In water; at 90℃; for 0.333333h;Green chemistry; General procedure: In a typicalprocedure,iodobenzene (1.0 mmol, 0.203 g), phenylboronicacid (1.2 mmol, 0.146 g), potassium carbonate(1.5 mmol, 0.207 g), ZrO2ECP-Pd nanocatalyst (0.31 mol%,0.005 g), and water (3 mL) were allowed to react at 90 C. Uponthe completion of the reaction which was monitored by TLC,the reaction mixture was cooled to room temperature and thecatalyst was separated by centrifuge. The resulting solution wasextracted with ethyl acetate (310 mL). The organic layerswere combined, dried with sodium sulfate, and filtered. Thefiltrate was concentrated by vacuum and purified by thinlayerchromatography usingn-hexane/ethyl acetate (50/1) to affordthe pure product (0.150 g, %98 yield).
90% With 0.1 % Cu/C; potassium carbonate; In water; at 50℃; for 3.5h;Green chemistry; General procedure: In a test tube, 1.0 mmol of aryl halides 1, 1.2 mmol of phenylboronic acid 2 were mixed together and then 2.0 mmol of K2CO3, and the Cu/Cnano-catalyst (0.1 mol % Cu) in 2 mL of H2O, were added in air. The reaction mixture was then stirred at 50 C for appropriate time. After completion of the reaction (monitored by TLC), the catalyst was removed by simple filtration. The recycled catalyst was was hed with ethanol and water (3 × 5 mL) and dried at 60 C in oven for further use. The aqueous layer was extracted with ethyl acetate, and organic layer dried over anhydrous MgSO4. The solvent was evaporated under reduced pressure to give the corresponding biaryl compounds.
90% With tetrabutylammomium bromide; potassium carbonate; In water; at 40℃; for 0.583333h; General procedure: Typically, a 10-mL round-bottom flask was charged withiodobenzene (1.0 mmol, 0.204 g), phenylboronic acid(1.1 mmol, 0.134 g), K2CO3(1.2 mmol, 0.165 g), TBAB(0.2 mmol, 0.064 g), H2O(3 mL) and 0.0015 g of γ-Fe2O3/AEPH2-TC-Pd (0.1 mol%). The resultant mixture was heatedunder stirring at 40 C for 10 min. After completion of thereaction (as judged by TLC), the reaction mixture wasallowed to cool down to room temperature and the nanocatalystwas easily separated by using a proper magnetic field,washed with EtOH and vacuum-dried at 50 C to be ready for utilizing in successive runs. Subsequently, the reactionmixture was extracted with ethyl acetate (5 × 5 mL). Combinedorganic phase was dried over anhydrous Na2SO4,andsolvent was next removed on a rotary evaporator. Thereafter,the obtained crude product was chromatographed on silicagel (eluted with n-hexane:ethyl acetate; 50:1), to afford thecorresponding pure product (0.148 g, % 98 yield).
85% With potassium carbonate; In water; at 60℃; for 3h;Catalytic behavior; General procedure: Aryl halide (1 mmol), arylboronic acid (1.2 mmol), K2CO3 (3 mmol) and 25 mg (0.07 mol%) Pdo-catalyst (Pdo-Mont.) were added to 10 ml of water and the reaction mixture was stirred at 60 C for a stipulated time period. The progress of the reactions was monitored by TLC. After completion of the reaction, the mixture was cooled to room temperature (∼25 C), and ethyl acetate (10 ml) was added to the mixture followed by separation of the solid catalyst by filtration through sintered funnel (G-3). The recovered catalyst was washed with acetone, dried in a desiccator and stored for another run. The organic extract was washed with water, dried over Na2SO4 and concentrated to give the crude products, which was finally purified by silica gel column chromatography using ethyl acetate and hexane as eluents. The products were identified by 1H NMR, mass spectrometry and melting point determination followed by their comparison with the standard literature data [54,55
85% With potassium carbonate; In water; at 80℃; for 0.75h; General procedure: Potassium carbonate (1.5 mmol, 0.207 g) was added to a mixture of iodobenzene (1.0 mmol, 0.203 g) and phenylboronic acid (1.2 mmol, 0.146 g), in water (3 mL) at 80 C. Then, to the resulting mixture ZrO2(at)AEPH2-PPh2-Pd(0) (0.2 mol%, 0.004 g) was added under stirring. After the completion of the reaction (20 min) which was monitored by TLC, the nanocatalyst was recovered by centrifugation, washed with ethyl acetate and dried under vacuum at 100 C for 24 h. The reaction mixture was then extracted with ethyl acetate (5 × 5 mL) and the combined organic layer was dried over anhydrous Na2SO4. After evaporation of the solvent, the crude product was purified by thin layer chromatography using n-hexane/ethyl acetate (50/1) to afford the pure product (0.145 g, % 95 yield).
84% With potassium carbonate; In ethanol; water; at 60℃; for 3h;Green chemistry; General procedure: A mixture of aryl halide (0.125mmol), phenylboronic acid(0.126mmol), K2CO3(0.187mmol), in 0.5ml H2O:EtOH(1:1) and Pd(II)NA2SMNP (0.0006g, 0.02mol%) wasstirred at 60C for the appropriate of time. The progressof the reaction was monitored by TLC. After completionthe reaction, the catalyst was removed with an externalmagnet and washed with EtOH, dried and used directly fora subsequent round of reaction without further purification.Then, desired product (liquid phase) was extracted byplate chromatography eluted with n-hexane/EtOAc (10:1).
45% With triethylamine; In neat (no solvent); at 70℃; for 4h;Sealed tube; Irradiation; General procedure: In a typical reaction, a mixture of aryl halid (0.2mmol),arylboronic acid (0.22 mmol), Et3N(0.4 mmol) and TiO2-AA-Pd nano hybrid (0.15mol%) was added in a10 mL Pyrex test tube and sealed with septum cap. Then thereaction mixture transferred into a reactor chamber and irradiate dunder magnetic stirring using a CFL lamp (philips,wavelength in the range 390-750nm, 40W, 1.1Wm-2) asthe visible light source at 70C for appropriate time. Aftercompletion of the reaction, TiO2-AA-Pd nanohybrid wasextracted by adding of ethanol (5mL) followed by centrifugingand decantation (3 × 5mL ethanol). Then, desired product(liquid phase) was extracted by plate chromatographyeluted with n-hexane/EtOAc (10/2).
With potassium carbonate; In water; for 2h;Reflux;Catalytic behavior; General procedure: To a mixture of Pd(II)-β-CD (0.001mol%, based on palladium, 0.23mL from a solution of 1mg in 100mL water, see Table2 for amount of catalyst) in 2mL water was added aryl halide (0.2mmol), arylboronic acid (0.24mmol), and K2CO3 (0.3mmol). The resulting mixture was stirred at reflux for 1-12h (Table2). After cooling, the product was extracted with n-hexane (2×3mL) and dried over Na2SO4. The product was purified by flash chromatography and characterized with 1H and 13CNMR (in CDCl3 and DMSO solvents) to afford biaryls 3a-s in 56-100% yields. All products are known and most of them are commercially available (see supporting information).

  • 9
  • [ 13331-27-6 ]
  • [ 369-57-3 ]
  • [ 2113-58-8 ]
  • 10
  • [ 2401-21-0 ]
  • [ 13331-27-6 ]
  • [ 847406-42-2 ]
YieldReaction ConditionsOperation in experiment
39% With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In ethanol; water; toluene; at 90℃; for 24h; A solution of 2,3-dichloro-iodobenzene (6.00 G, 22. 0 mmol) in 60 mL toluene and 20 mL eth- anol was treated with 3-nitro-phenylboron. ic acid (4. 22 G, 25. 3 mmol) and NA2CO3 (2 N in H20, 30. 0 ML). Then mixture was purged with N2 for 5 min and Pd- (PPH3) (1. 02 G, 0. 879 mmol) was added. The mixture was heated to 90°C for 24 h and cooled to ambient temperature and concentrated in vacuo. The residual oil was partitioned with Et2O (80 M. L) and washed with dilute brine solution (3x50 mL), dried (Na2SO4), filtered, and concentrated under reduced pressure. The resulting white solid was recrystallized from hexane and to give the title compound (2.30 g, 39percent) as a fluffy white SOLID. 1H NMR (CDC13,400 MHz) 5 8.29 (m, 2H), 7.76 (m, 1H), 7.63 (t, J=7. 61 Hz, 1H), 7. 55 (m, 1H), 7. 31 (t, J=7.81 HZ, 1H), 7.26 (m, 1H.)
  • 11
  • [ 13331-27-6 ]
  • [ 71-43-2 ]
  • [ 2113-58-8 ]
  • 12
  • [ 74137-36-3 ]
  • [ 13331-27-6 ]
  • [ 1155890-29-1 ]
  • 14
  • [ 1445-39-2 ]
  • [ 13331-27-6 ]
  • [ 1111104-92-7 ]
  • 15
  • [ 13331-27-6 ]
  • [ 145691-59-4 ]
  • [ 1397270-97-1 ]
  • 16
  • [ 557-93-7 ]
  • [ 13331-27-6 ]
  • [ 63744-25-2 ]
  • [ 1412909-08-0 ]
  • 17
  • [ 3199-50-6 ]
  • [ 13331-27-6 ]
  • [ 56656-35-0 ]
YieldReaction ConditionsOperation in experiment
32.5% With tetrabutylammomium bromide; palladium diacetate; potassium carbonate; In water; at 70℃; for 3.33h;Inert atmosphere; General procedure: Mixtures of the aryl bromides 24 or 30 (2.65mmol), the boronic acids 23a or 23b (2.23mmol), tetrabutylammonium bromide (796mg, 2.47mmol), and K2CO3 (2.9g, 21mmol) were suspended in distilled water (10mL) under argon for 20min. Then Pd(OAc)2 (9.2mg, 0.04mmol) was added, and the resulting suspensions were heated to 70C and stirred under argon for 3h. After cooling down, the solutions were diluted with distilled water (10mL) and extracted with CH2Cl2 (3×15mL). The combined organic layers were dried over Na2SO4 and the solvents were evaporated. The crude residues were further purified by silica gel column chromatography, eluting with hexane-ethyl acetate 8:2, to provide the products 25a-b or 25d.
  • 18
  • [ 13331-27-6 ]
  • [ 100-63-0 ]
  • [ 2113-58-8 ]
YieldReaction ConditionsOperation in experiment
72% With bis-triphenylphosphine-palladium(II) chloride; sodium dodecyl-sulfate; potassium carbonate; p-toluenesulfonyl chloride; In water; at 60℃; General procedure: A mixture of arylhydrazine 1 (0.24mmol, 1.2equiv.), aryl boronic acid 2 (0.2 mmol), K2CO3(0.6 mmol, 3.0 equiv.), p-toluenesulfonylchloride (0.24 mmol, 1.2 equiv.), sodium dodecyl sulfate (0.02 mmol, 10 mol %), and PdCl2(PPh3)2(0.01 mmol, 5 mol %) was stirred at 60 C in water (2.0 mL) for 4-8 h under air.After completion of the reaction (indicated by TLC), the mixture was quenched with saturatedNaCl solution, extracted by EtOAc,and dried with Na2SO4. The crude product was purified by flash columnchromatography to provide the corresponding product 3.
  • 19
  • [ 13331-27-6 ]
  • N’-phenylmethanesulfonohydrazide [ No CAS ]
  • [ 2113-58-8 ]
  • 20
  • [ 13331-27-6 ]
  • [ 84539-22-0 ]
  • 2-morpholino-5-(3-nitrophenyl)pyrimidine [ No CAS ]
YieldReaction ConditionsOperation in experiment
57% With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In tetrahydrofuran; water; at 155℃; for 0.333333h; General procedure: To a mixture of compound 7a (1 mmol), the corresponding (het)arylboronic acid 8 (1.2 mmol), Pd(PPh3)4 (58 mg, 0.05 mmol) in degassed THF (3 mL), a solution of K2CO3 (346 mg, 2.5 mL) in water (4 mL) were added. The reaction mixture was microwave irradiated at 155 C (250 W) for 20 min, then solvent was removed in vacuo. Products were isolated by column chromatography (elution with ethyl acetate-hexane, 1 : 2).
  • 21
  • [ 221044-05-9 ]
  • [ 13331-27-6 ]
  • 2-(3-nitrophenyl)-1-(pyrimidin-2-yl)-1H-indole [ No CAS ]
YieldReaction ConditionsOperation in experiment
97% With dichloro(pentamethylcyclopentadienyl)rhodium (III) dimer; silver trifluoroacetate; In methanol; at 60℃;Schlenk technique; Inert atmosphere; General procedure: A mixture of N-pyrimidyl indoles 1 (0.20 mmol, 1.0 equiv.), arylboronicacids 2 (0.40 mmol, 2.0 equiv.),AgOOCF3 (0.80 mmol, 4.0 equiv.), and [RhCp*Cl2]2(0.002 mmol, 0.01 equiv.) were combined in MeOH (1.0 mL) in a dried Schlenk tubeunder a argon atmosphere. The resulting mixture was stirred at 60 C andmonitored by TLC. Uponcompletion or no further improvement of reaction, the reaction mixture wascooled to room temperature and added with Et3N (1 mL). Then themixture was filtered through a pad of silica gel eluting with 25 mL of CH2Cl2.The solvent was removed under reduced pressure and the residue was purified byflash chromatography on silica gel to afford the desired products.
  • 22
  • [ 13331-27-6 ]
  • trifluoromethanesulfonic acid diphenyl(trifluoromethyl)sulfonium salt [ No CAS ]
  • [ 2113-58-8 ]
  • 23
  • [ 13331-27-6 ]
  • [ 873-55-2 ]
  • [ 2113-58-8 ]
  • 24
  • [ 13331-27-6 ]
  • [ 35691-20-4 ]
  • 2-(3-nitrophenyl)-4-(pyrrolidin-1-yl)pyrimidine [ No CAS ]
  • 25
  • [ 13331-27-6 ]
  • [ 34259-99-9 ]
  • 4‐(3‐nitrophenyl)‐1,3‐thiazole [ No CAS ]
  • 26
  • [ 105486-72-4 ]
  • [ 13331-27-6 ]
  • ethyl 1-methyl-5-(3-nitrophenyl)pyrazole-4-carboxylate [ No CAS ]
YieldReaction ConditionsOperation in experiment
60% With bis-triphenylphosphine-palladium(II) chloride; sodium carbonate; In 1,2-dimethoxyethane; water; at 90℃; A solution of ethyl 5-bromo-l-methylpyrazole-4-carboxylate (1.0 g, 4.29 mmol), 3- nitrophenylboronic acid (859 mg, 5.15 mmol), sodium carbonate (909 mg, 8.58 mmol dissolved in 4.3 mL water), and bis(triphenylphosphine)palladium(II) dichloride (151 mg, 0.21 mmol) in DME (43 mL) was heated to 90 C overnight. After this time, General Work-up Procedure 1 was followed, and the crude residue was purified by Chromatography A to afford the title compound (710 mg, 60 % yield).
  • 28
  • [ 1885-32-1 ]
  • [ 13331-27-6 ]
  • 8-methyl-2-(3-nitrophenyl)-2,3-dihydrobenzo[d][1,3,2]diazaborinin-4(1H)-one [ No CAS ]
 

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