Structure of 1242770-51-9
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| CAS No. : | 1242770-51-9 |
| Formula : | C14H18BBrO2 |
| M.W : | 309.01 |
| SMILES Code : | CC1(C)C(C)(C)OB(/C=C/C2=CC=C(Br)C=C2)O1 |
| English Name : | (E)-2-(4-Bromostyryl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane |
| MDL No. : | MFCD12546200 |
| InChI Key : | KOKMZNDSHKZFHO-MDZDMXLPSA-N |
| Pubchem ID : | 46900787 |
* 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.

| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 82% | With potassium fluoride; 18-crown-6 ether In 1,4-dioxane at 100℃; for 9h; Inert atmosphere; |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 82% | With KF; 18-crown-6 In 1,4-dioxane 1-PhOC(O)OCH2-2-(Me3SiCH2)C6H4, 2-((E)-(4-BrPh)-CH=CH)-(4,4,5,5-Me4-dihydro-1,3,2-dioxaborol), KF, 18-crown-6 (3:2:3.3:3.3 mol) heated in dioxane soln. at 100°C for 9 h; |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 73% | With NaOC(CH3)3; CH3OH In tetrahydrofuran 1.0 mol% Cu-complex, alkyne, diborane, NaOC(CH3)3, CH3OH, THF, -15°C, 24 h, N2 atm.; 91:9 ratio of isomers; |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 98% | With potassium hydrogen bifluoride In water; acetonitrile at 0 - 20℃; for 2.08333h; |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 82% | In tetrahydrofuran; water at 20℃; |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 97% | Stage #1: pinacolborane With C32H41CuN2O2S In toluene at 20℃; for 0.25h; Schlenk technique; Inert atmosphere; Stage #2: 4-bromo-1-ethynylbenzene In toluene at 20℃; for 2h; Schlenk technique; Inert atmosphere; stereoselective reaction; | |
| 94% | With sodium triethylborohydride; scandium tris(trifluoromethanesulfonate) In tetrahydrofuran; toluene at 100℃; for 24h; Microwave irradiation; Inert atmosphere; regioselective reaction; | |
| 94% | With lithium triethylborohydride; C76H65Cl2CoN3 In neat (no solvent) at 80℃; for 18h; Schlenk technique; Inert atmosphere; |
| 89% | With [RuHCl(CO)(PPh3)3] at 60℃; for 3h; Schlenk technique; Inert atmosphere; stereoselective reaction; | |
| 88% | at 60℃; for 16h; Inert atmosphere; Schlenk technique; | |
| 86% | With [RuHCl(CO)(PPh3)3] In toluene at 50℃; for 16h; Inert atmosphere; | |
| 85% | With zinc trifluoromethanesulfonate; sodium triethylborohydride In tetrahydrofuran; toluene at 80℃; for 10h; Schlenk technique; Inert atmosphere; regioselective reaction; | |
| 85% | With tropylium tetrafluoroborate In neat (no solvent) at 70℃; for 12h; Inert atmosphere; | |
| 82% | With dibutylmagnesium In n-heptane; toluene at 80℃; for 18h; Inert atmosphere; regioselective reaction; | |
| 82% | With 8C4H8O*10Br(1-)*5Co(2+)*2C14H10N8; sodium triethylborohydride In tetrahydrofuran; tert-butyl methyl ether at 45℃; for 10h; Inert atmosphere; Schlenk technique; regioselective reaction; | |
| 78% | With trimethylsilylmethyllithium In neat (no solvent) at 90℃; for 8h; Schlenk technique; Glovebox; Inert atmosphere; | |
| 76% | In neat (no solvent) at 110℃; for 12h; Inert atmosphere; | |
| 75% | With silver(I) acetate In toluene at 120℃; for 18h; Schlenk technique; Inert atmosphere; stereoselective reaction; | |
| 74% | With C30H26Br4Fe2N6; sodium t-butanolate In toluene at 25℃; Sealed tube; Inert atmosphere; Glovebox; stereoselective reaction; | |
| 58% | With LDBBA In neat (no solvent) at 50℃; for 15h; Inert atmosphere; | |
| 54% | With C27H44N3Si3V In diethyl ether at 20℃; for 16h; Inert atmosphere; regioselective reaction; | |
| 46% | With Lithium 1,1,1,3,3,3-hexamethyldisilazide In toluene at 100℃; for 24h; Inert atmosphere; Glovebox; Schlenk technique; | |
| 37% | With CoH{PPh(OEt)2}4 In tetrahydrofuran Schlenk technique; Inert atmosphere; Irradiation; diastereoselective reaction; | 4. General procedure and characterization data of reduction products General procedure: In an oven-dried vial the cobalt catalyst (1 mol%, 2 μmol, 1.7 mg) and a stirring bar were introduced. A cap with rubber septum was used to close the vial and the system was then purged with Argon. THF (0.2 mL, 1.0M), alkyne (1.0 equiv, 0.2 mmol) and HBPin (1.1 equiv, 0.22 mmol, 32 μL) were then successively added and the mixture was stirred overnight under irradiation of blue LED light. After this time, the solution was diluted with Et2O and washed two times with distilled water, the combined aqueous layers were extracted two timeswith Et2O and the combined organic layers were washed with brine, dried (MgSO4), filtered and concentrated under vacuum. The crude material was purified by column chromatography to afford the titled compounds. |
| 32% | Stage #1: pinacolborane With 1,3-bis-(diphenylphosphino)propane; cobalt acetylacetonate In tetrahydrofuran at 20℃; for 0.25h; Inert atmosphere; Schlenk technique; Stage #2: 4-bromo-1-ethynylbenzene In tetrahydrofuran at 50℃; for 46h; Inert atmosphere; Schlenk technique; | |
| In neat (no solvent) at 110℃; for 14h; | ||
| With [RuHCl(CO)(PPh3)3] In toluene at 100℃; for 3h; Schlenk technique; Inert atmosphere; | ||
| 302.9 mg | With C20H22AlN2PSe In toluene at 30℃; for 8h; Schlenk technique; Glovebox; Inert atmosphere; chemoselective reaction; | |
| at 215℃; for 0.3h; Schlenk technique; Inert atmosphere; Microwave irradiation; | ||
| 34 %Chromat. | With sodium triethylborohydride for 1h; Schlenk technique; Inert atmosphere; Sealed tube; regioselective reaction; | 2.2. General procedure of NaHBEt3-catalysed hydroboration General procedure: 1.0 mmol of alkyne, 0.1 mL of decane and 1.1 mmol of pinacolborane,were placed in previously evacuated Schlenk bomb flask fitted witha plug valve. A reference sample was taken. Next, 0.1 mL of 1 M solutionof NaHBEt3 (0.1 mmol) in toluene was added, reaction vessel was closedand heated at 60 C with stirring. After specified time, reaction mixturewas cooled down to the room temperature and analysed using GC andGC-MS. Products of hydroboration were isolated by extraction with 1mL of DCM followed by column chromatography of concentrated extract(SiO2, hexane/Et2O, 98:2). |
| 68 %Spectr. | With C43H65MgNOP2 In neat (no solvent) at 80℃; for 18h; Inert atmosphere; Schlenk technique; Glovebox; regioselective reaction; | |
| With C36H72B3P7Si3 In benzene-d6 at 50℃; Schlenk technique; Inert atmosphere; Glovebox; | ||
| 66% | With Schwartz's reagent In dichloromethane at 20℃; Inert atmosphere; | |
| 99 %Spectr. | With [bis(phosphinimino)amide AlH]+[B(C6F5)4]- In benzene at 60℃; Glovebox; Schlenk technique; | |
| 55 % | With C31H50NO2Si2Y In toluene at 110℃; Inert atmosphere; Schlenk technique; Glovebox; regioselective reaction; | |
| 86 % | With manganese(II) bromide; sodium triethylborohydride In hexane at 70℃; Inert atmosphere; Sealed tube; chemoselective reaction; | |
| 84 % | With C38H30ClNOP2Pt In tetrahydrofuran at 50℃; Inert atmosphere; Schlenk technique; stereoselective reaction; | |
| 75 % | With sodium triethylborohydride; C9H13Cl2CoN6 In tetrahydrofuran at 20℃; Inert atmosphere; Schlenk technique; | |
| With Triethoxysilane In 1,4-dioxane at 80℃; for 24h; regioselective reaction; |

| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| With sodium periodate; ammonium acetate In water; acetone Inert atmosphere; |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 93% | Stage #1: bis(pinacol)diborane With DPEPhos; copper(l) chloride; sodium t-butanolate In tetrahydrofuran at 25℃; for 0.166667h; Schlenk technique; Inert atmosphere; Stage #2: 4-bromo-1-ethynylbenzene In tetrahydrofuran; methanol at 25℃; Schlenk technique; Inert atmosphere; Sealed tube; | |
| 91% | With sodium methylate; Cu(2+)*4Cu(1+)*4I(1-)*2C5H3N2O2(1-)*C5H5N*C2H7N*3C3H7NO In ethanol at 25℃; for 1h; Inert atmosphere; | 2.3. Typical procedure for the hydroborylation of alkynes General procedure: The typical experimental procedure for the hydroborylation ofalkynes is as follows: a mixture of alkyne (2 mmol), compound 1(0.006 mmol), bis(pinacolato)diboron (2.5 mmol), NaOMe(0.2 mmol) and 5 mL EtOH were successively added into a reaction flask equipped with a Ar (99.99%) balloon. Then the flask was vacuumedand charged in Ar three times to exclude air in the reactionsystem. Subsequently, the obtained reaction mixture was magneticallystirred at 25 °C for 1 h. After the reaction was completed, thecatalysts were separated by filtration and the yield was determinedby GC analysis. The pure products were obtained by columnchromatography on silica gel (petroleum ether/ethyl acetate as aneluent). |
| 90% | With potassium methanolate In acetonitrile at 20℃; for 2h; Inert atmosphere; |
| 83% | With [Cu(phen)(xantphosTEPD)]PF6; potassium carbonate In water; acetonitrile at 20℃; for 7h; Sealed tube; Inert atmosphere; Irradiation; diastereoselective reaction; | |
| 80% | With 2.9 weight% Cu(II) loaded porous coordination network-222 nanoparticles In ethanol; water at 80℃; Sealed tube; regioselective reaction; | 4.2. Catalytic performance test of PCN-222(Cu) with different particlesizes General procedure: Taking the synthesis of 2a for example: PCN-222(Cu, 1200 nm)(1.5 mol%) was used as catalyst, 4-methylphenylacetylene 1a(22 lL, 0.2 mmol) and B2pin2 (76 mg, 0.4 mmol) were dispersed in solvent (1 mL, VEtOH : VH2O = 3 : 7) in a sealed tube, which were kept in 80 °C for 5 h. The conversion was determined by GC-MS.After the reaction was finished, the reaction mixture was cooled to room temperature and concentrated in vacuum. Purification of the crude product with flash column chromatography (silica gel;Petroleum ether:EtOAc = 100:1-50:1) gave product 2a. |
| 79% | With potassium carbonate; 6Cu(1+)*3C20H14N6O4(2-) In water; acetonitrile at 25℃; for 0.333333h; stereoselective reaction; | |
| 79% | With water; potassium carbonate; 6Cu(1+)*3C20H14N6O4(2-) In acetonitrile at 25℃; for 0.333333h; stereoselective reaction; | |
| 74.4% | With methanol; potassium <i>tert</i>-butylate; [CuI(4,7-di(1H-imidazole-1-yl)benzo[c][1,2,5]thiadiazole)]n at 25℃; for 1h; Schlenk technique; | |
| 68% | With tetrabutylammonium tetrafluoroborate In methanol at 20℃; Electrochemical reaction; | |
| 68% | With tetrabutylammonium tetrafluoroborate In methanol | |
| 33% | With sodium t-butanolate In methanol at 50℃; for 20h; | |
| With methanol; DPEPhos; copper(l) chloride; sodium t-butanolate In tetrahydrofuran at 20℃; for 12h; Inert atmosphere; Glovebox; Sealed tube; | ||
| 85 % | With ethanol at 30℃; Autoclave; Inert atmosphere; | |
| 93 % | With cerium(IV) oxide; potassium methanolate In methanol; toluene at 50℃; Inert atmosphere; | |
| 85 % | With methanol; N-propyl-N-(2-(pyridin-2-ylamino)phenyl)formamide In tetrahydrofuran at 60℃; Schlenk technique; stereoselective reaction; | |
| 66 % | With methanol; sodium t-butanolate In tetrahydrofuran at 60℃; Inert atmosphere; Schlenk technique; Glovebox; |

| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 77% | With dimethyl zinc(II) In N,N-dimethyl-formamide at 60℃; for 3h; Inert atmosphere; |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 77% | With copper(II) trifluoroacetate; sodium carbonate In 1,4-dioxane at 80℃; for 18h; Inert atmosphere; regioselective reaction; | General procedure for the synthesis of (E)-4,4,5,5-tetramethyl-2-styryl-1,3,2-dioxaborolane (3a) General procedure: A Schlenk tube with a magnetic stirring bar was charged with 3-phenylpropiolic acid (1a, 68 mg, 0.5 mmol), bis(pinacolato)diboron (2a, 152 mg, 0.6 mmol), Cu(TFA)2 (29 mg, 10 mol%), Na2CO3 (127 mg, 1.2 mmol), and 1,4-dioxane (2 mL) under N2. The reaction mixture was stirred at 80 °C for 18 h (monitored by TLC and GC). Upon completion of the reaction, the reaction mixture was then cooled to ambient temperature, diluted with ethyl acetate (20 mL), filtered through a plug of silica gel, and washed with ethyl acetate (20 mL). The organic layer was washed with saturated brine (20 mL×2) and dried over anhydrous Na2SO4. The solvents were removed via rotary evaporator and the residue was purified by flash chromatography (silica gel, ethyl acetate: petroleum ether=1:30) to give 89.7 mg of desired product 3a in 78 % yield as a colorless oil. 1H NMR (400 MHz, CDCl3): δ 7.48-7.50 (m, 2H), 7.41 (d, 1H, J=18.5Hz), 7.29-7.32 (m, 3H), 6.18 (d, 1H, J=18.4Hz), 1.32 (s, 12H). 13C NMR (100 MHz, CDCl3): δ 148.5, 136.4, 127.9, 127.5, 126.0, 82.3, 23.8 |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 92% | With carbonylchlorohydridobis(tricyclohexylphosphine)ruthenium(II) In toluene at 80℃; for 5h; Schlenk technique; Inert atmosphere; | |
| 82% | With Ru(CO)(Cl)H(PCy3)2 at 110℃; for 18h; Schlenk technique; Inert atmosphere; Green chemistry; stereoselective reaction; | 2.2.2. Borylative coupling under repetitive batch mode - Aliphaticsolvent extraction General procedure: A 50 mL Schlenk vessel was charged with dried PEG (1 g) and[Ru(CO)Cl(H)(PCy3)2] (0.01 mmol) under an argon atmosphere. Subsequently, vinyl boronate (0.5 mmol) and olefin (1.0 mmol)were added. The reaction was carried out for 18 h at 110 °C. Thereaction mixture was cooled to room temperature and the products were extracted with aliphatic solvent: n-hexane or n-heptane(3 5 mL) and analyzed by GC-MS analysis. The residual amount of solvent was evaporated under a vacuum and a new portion of substrates was added under an argon atmosphere, and subsequent batches and extractions were carried out under the above-described conditions. |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 77.778 % de | Stage #1: (E)-1-(4’,4’,5’,5’-tetramethyl)-1’,3’,2’-dioxaboronalyl-2-(4’’-bromophenyl)ethene With bromine In diethyl ether; dichloromethane for 0.666667h; Stage #2: With sodium methylate In methanol; diethyl ether; dichloromethane at -20℃; for 2h; Overall yield = 84 %; stereoselective reaction; | |
| 80 % de | Stage #1: (E)-1-(4’,4’,5’,5’-tetramethyl)-1’,3’,2’-dioxaboronalyl-2-(4’’-bromophenyl)ethene With sodium methylate In diethyl ether at -20℃; for 0.666667h; Stage #2: With bromine In diethyl ether; dichloromethane at -20℃; for 2h; Overall yield = 89 %; stereoselective reaction; |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 79% | Stage #1: (E)-1-(4’,4’,5’,5’-tetramethyl)-1’,3’,2’-dioxaboronalyl-2-(4’’-bromophenyl)ethene With sodium hydroxide In diethyl ether; water at 0℃; Stage #2: With iodine In diethyl ether; water at 0℃; for 0.5h; stereoselective reaction; |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 81% | With tetrakis(actonitrile)copper(I) hexafluorophosphate; (S,S)-2,2'-isopropylidenebis(4-phenyl-2-oxazoline) In dichloromethane at 25℃; for 8h; Inert atmosphere; Schlenk technique; stereoselective reaction; |

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