4-(4,4,5,5-TETRAMETHYL-1,3,2-DIOXABOROLAN-2-YL)FLUOROBENZENE

In the stirring step, potassium acetate (KOAc) (0.073 g, 0.09 mmol) was added to a solution of 1, 1'-bis (diphenylphosphino) ferrocene-palladium (II) dichloride-dichloromethane complex (PdCl 2 (dppf) CH 2 Cl 2) Fluorophenyl bromide 1b (R═F, 0.613 g, 3.5 mmol) and bis (pinacolato) diboron 2 (1.161 g, 4.5 mmol) were added to a dimethylsulfoxide (DMSO) solution in which 1.601 g The mixture was stirred at 80 ° C. for 1.5 hours to obtain a reaction solution.In the organic layer extraction step, ice water is added to the reaction solution after the stirring step, and the organic layer is extracted with ethyl acetate (EtOAc) (80 mL × 2) to obtain an extract.In the concentration step, the extract solution subjected to the organic layer extraction step is dried with anhydrous magnesium sulfate (MgSO 4) and concentrated under reduced pressure to obtain a residue.In the purification step, the residue subjected to the concentration step was purified by column chromatography (silica gel, hexane / EtOAc = 9: 1) to obtain the target compound (2- (4-fluorophenyl) -4, 4, 5, 6- Methyl-1, 3, 2-dioxaboron 3b (R = F)) in a yield of 93percent.A flask charged with 1 (1.226 g, 7.0 mmol), borate 2 (PinGeneral procedure: tert-Butyl nitrite (155 mg, 1.1 mmol) wasadded drop wise to a mixture of bis(pinacolato)diborane (127 mg, 0.5 mmol), 4-anisidine (61 mg, 0.5 mmol) and eosin Y (0.01 mmol) in acetonitrile (3 mL).The resulting mixture was stirred at room temperature under irradiation withblue LED for 2 h (TLC). This mixture after being diluted with ethyl acetate(5 mL) was ltered through celite and the ltrate was extracted with ethylacetate (3 10 mL). The extract was washed with brine, dried over anhydrousNa 2 SO 4 , and evaporated to leave the crude product which was puried bycolumn chromatography over silica gel with hexane–ethyl acetate (98:2) aseluent to furnish pure 2-(4-methoxyphenyl)-4, 4, 5, 5-tetramethyl-1, 3, 2-dioxaborolane as a light yellow viscous liquid (3d, 208 mg, 88percent); IR (neat)2978, 2933, 2839, 2526, 2050, 1950, 1911, 1724, 1605, 1570 cm1;1H NMR(500 MHz, CDCl 3 ) d 1.33 (s, 12H), 7.82 (s, 3H), 6.89 (d, J = 8.0 Hz, 2H), 7.75 (d, J = 8.0 Hz, 2H);13C NMR (125 MHz, CDCl 3 ) d 24.9 (4C), 55.2, 83.6 (2C), 113.4(2C), 136.6 (2C), 162.3. The spectroscopic data is in full agreement with thosereported for an authentic sample.14This procedure was followed for all thereactions listed in Table 2. All of these products (3a, 143b, 143c, 16a3d, 143e, 143f, 8a3g, 143h, 143i, 143j, 8a3k, 8a3l, 8a3m, 143n, 8c3o, 16b) are known compounds, and their spectroscopic data are in agreement with those previously reported.General procedure: Aryl amine (10 mmol) was dissolved in a mixture of 5 mL of distilled water and 3.4 mL of 50percent hydrofluoroboric acid. After cooling the reaction mixture to 0 °C using ice bath and the sodium nitrite (0.69 g in 2 mL distilled water), was added dropwise in 5 min interval of time. The resulting mixture was stirred for 1 h and the precipitate was collected by filtration and redissolved in minimum amount of acetone. Diethylether was added until precipitation of aryl diazonium tetrafluoroborate, which is filtered, washed several times with diethyl ether and dried under vacuum. Typical reaction procedure: General procedure: Diazonium tetrafluoroborate salts (0.5 mmol) and BGeneral procedure: To a solution of arylamine (0.5 mmol, 1.0 equiv) in MeOH(1.0 mL) was added HCl (0.5 mL, 1.5 mmol, 3.0 equiv) followed by H2O (0.5 ml). This mixture was stirred 2 min, and the NaNO2 solution (0.25 mL) was then added. The NaNO2 solution was prepared by dissolving 35 mg of NaNO2 in H2O (0.25 mL). This mixture was stirred 30 minat 0–5 °C followed by B2pin2 (2, 381 mg, 1.5 mmol, 3.0equiv) in MeOH (1.0 mL). This mixture was stirred 60 min.H2O (10 mL) was added to the reaction mixture, then extracted with CH2Cl2 (50 mL, 3×). The combined organic layers were washed with sat. NaHCO3, dried over Na2SO4, followed by evaporation, and the crude residue was purified by flash chromatography.General procedure: An oven-dried Schlenk tube, containing a Teflon-coated magnetic stir bar was charged with CsF (228 mg, 1.5 mmol, 3 equiv) and bispinacolatodiboron (254 mg, 1 mmol, 2 equiv). Under an argon atmosphere, freshly distilled DMSO (0.4 mL), the appropriate aryl iodide (0.5mmol), and pyridine (0.4 to 1 equiv) were added successively. The reaction mixture was heated to 105 °C and stirred for 2 h under argon.General procedure: 4-Iodoanisole (0.813 mmol, 200 mg), bis(pinacolato)diboron (1.219 mmol, 309 mg) were dissolved in 3 mL of dmf followed by copper ferrite nanoparticles (5molpercent with respect to 4-iodoanisole) and potassiumtert-butoxide (1.219 mmol, 137 mg) were added to a 10 mLcapped vial and stirred at RT for time indicated. After stirring, the mixture was diluted with diethyl ether and filtered through celite bed. The filtrate was extracted with water (3 times) and the organic phase was dried over anhydrous MgSO4. The crude product was subjected to analyze by GC–MS. The conversion yield is accurately measured based on the consumption of 4-iodoanisole and the side product formed due to protodeiodination.Fluoro-4-iodobenzene (44 mg, 0.20 mmol), 1, 1-diboxomethane (107 mg, 0.40 mmol)And sodium tert-butoxide base (38 mg, 0.40 mmol) was placed in a 4 mL vial.Toluene / tetrahydrofuran (2.0 mL, 1: 1 mixed solution) was then added.This vial was sealed for 6 hours at 80 ° C sealed with a PTFE / silicone coated capThe reaction proceeded. The reaction solution was then filtered through celite using dichloromethane, This organic material was concentrated under reduced pressure. The subsequent productsIn condition Φ 2.0 cm x 8 cm After silica gel column chromatography, n-hexane: diethyl ether, 15: 1 eluent.The results showed that 2- (4-Fluorophenyl) -4, 4, 5, 5, -tetramethyl-1, 3, 2-dioxaborolaneA boronated compound was produced. (28 mg, 63percent yield);General procedure: In a flask containing the appropriate boronic acid 1a-m (0.25 mmol) in tetrahydrofuran (THF; 3 mL) was added montmorillonite K10 (150percent m/m) followed by pinacol(30 mg, 0.25 mmol). The mixture was stirred for 15 minto homogenize the contents, and powdered 4 Å molecularsieves (150percent m/m) were added. The mixture was then stirredat room temperature for the time indicated in Scheme 2.After this period, the mixture was extracted with EtOAc(3 × 10 mL) and the organic phase was washed with water(2 × 15 mL). The organic phase was dried over anhydrousMgSO4, filtered and the solvent was removed in vacuo.General procedure D for the synthesis of the arylpinacolboronates by arylation of diisopropylaminoborane, catalysed by ferrocene (1percent), followed by methanolysis and transesterification In a dried tube reactor under argon as described in example 2, the arenediazonium salt (1 mmol) and the ferrocene (ΙΟμιηοΙ, 1.8mg) were dissolved in 2mL of anhydrous CHGeneral procedure: A mixture of 1 (0.369 mmol), 2 (0.369 or 0.554 mmol) and eosin Y (11.96 mg; 5 mol percent)was mixed in a 25 mL PMMA milling jar with 15 ZrO2 balls of 5 mm in diameter at 25 Hz.Irradiation of the reaction mixture was achieved by wrapping the milling jar with a greenLED strip (90 cm; see picture in section 2). After the milling was stopped, the reactionmixture was recovered from the milling jar and the product was purified by columnchromatography (SiO2, eluent 100:1 n-pentane/ethyl acetate).In a reaction flask charged with Pd(OAc)In a reaction flask charged with Pd(OAc)

Molecular Weight:222.07
Hydrogen Bond Acceptor Count:3
Rotatable Bond Count:1
Exact Mass:222.1227381
Monoisotopic Mass:222.1227381
Topological Polar Surface Area:18.5
Heavy Atom Count:16
Complexity:244
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes