Structure of 871125-84-7
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| CAS No. : | 871125-84-7 |
| Formula : | C14H18BClO2 |
| M.W : | 264.56 |
| SMILES Code : | CC1(C)C(C)(C)OB(/C=C/C2=CC=CC(Cl)=C2)O1 |
| English Name : | (E)-2-(3-Chlorostyryl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane |
| MDL No. : | MFCD08276867 |
| InChI Key : | NZBKTAJNGYXYSQ-CMDGGOBGSA-N |
| Pubchem ID : | 16218161 |
* 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 |
|---|---|---|
| With potassium carbonate In ethanol; water at 150℃; for 0.25h; Irradiation with microwave; | 25 Example 4B (100 mg, 0.25 mmol) was added to a Biotage microwave tube. (E)-2-(3- chlorostyryl)-4,4,5,5-tetramethyl-l,3,2-dioxaborolane (80 mg, 0.30 mmol) was added followed by ethanol (2mL) and potassium carbonate (0.15 mL, 2 M aqueous solution). FC 1007 (35 mg, 0.36mmol/g, Johnson Matthey) was added to the mixture, and the reaction mixture was heated in a microwave (Biotage Initiator) at 150 0C for 15 minutes. The reaction mixture was passed through a 2 g Si-carbonate cartridge (SiliCylcle) eluting with methanol. The collected eluate was concentrated. To this, 1 mL of dioxane and HCl in dioxane (0.63 mL, 4 M solution) was added, and the mixture was shaken at room temperature overnight. The resulting mixture was concentrated and purified by preparative HPLC. 1H NMR (500 MHz, DMSO-J6) ppm 9.79 (s, 1 H), 9.20 (br, 2H), 7.20 - 7.46 (m, 6 H), 6.99 (d, J=7.93 Hz, 1 H), 3.56 - 3.64 (m, 2 H), 3.30 - 3.46 (m, 4 H), 2.94 - 3.15 (m, 2 H), 2.68 (dd, J=13.58, 7.17 Hz, 1 H); MS (DCI+) m/z 354.2 (M+H)+. |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 50% | With caesium carbonate In 1,4-dioxane at 100℃; for 0.5h; Microwave irradiation; | 22.e Cesium carbonate (0.143 g, 0.438 mmol), palladium tetrakis (0.051 g, 0.042 mmol) and 2-[(E)-2-(3-Chloro-phenyl)- vinyl]-4,4,5,5-tetramethyl-[1,3,2]dioxaborolane (0.116 g, 0.440 mmol) were added to a solution of 2-(2-lodo-pyrimidin-4-yl)-1-methyl-4-oxo-1,4,6,7-tetrahydro-pyrrolo[3,2-c]pyridine-5-carboxylic acid tert-butyl ester (synthesised as reported in Example 9) (0.100 g, 0.22 mmol) in dioxane (5.0 ml) under argon atmosphere. Argon was bubbled for 5 minutes, the vial was closed and the reaction mixture was heated by microwave irradiation for 30 minute at 1000C for two cycles. In order to affect completion, a refresh of the catalyst and the base and two more cycles at the microwaves were carried on. The solvent was removed under vacuum, the residue was taken into DCM (5.0 ml), which was washed with a saturated solution of NaHCO3 (1 x 5.0 ml), brine (1 x 5.0 ml), and it was dried overNa2SO4. The filtrate was evaporated to dryness to give the crude product, which was purified by flash chromatography, over silica gel, using DCM/MeOH (9.9:0.1) as eluent, to afford 2-{2-[(E)-2-(3-Chloro-phenyl)-vinyl]- pyrimidin-4-yl}-1-methyl-4-oxo-1,4,6,7-tetrahydro-pyrrolo[3,2-c]pyridine-5-carboxylic acid tert-butyl ester yellow solid(0.051 g, 0.110 mmol, 50%). |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 83% | With dibutylmagnesium In n-heptane; toluene at 80℃; for 18h; Inert atmosphere; regioselective reaction; | |
| 81% | With Lithium 1,1,1,3,3,3-hexamethyldisilazide In toluene at 100℃; for 24h; Inert atmosphere; Glovebox; Schlenk technique; | |
| 55% | With p-N,N-dimethylaminobenzoic acid In neat (no solvent) at 120℃; for 0.25h; Microwave irradiation; stereoselective reaction; |
| 98 %Spectr. | With 2Fe(1+)*9CO In toluene at 100℃; for 24h; Inert atmosphere; | |
| 48 %Spectr. | With MIL-53(Al) metal-organic framework-CoH In neat (no solvent) at 90℃; for 22h; | |
| 80 %Spectr. | With [Cu(OH)(IPr)] In neat (no solvent) at 20℃; for 24h; | |
| 83 % | With C31H50NO2Si2Y In toluene at 110℃; Inert atmosphere; Schlenk technique; Glovebox; regioselective reaction; | |
| 70 % | With manganese(II) bromide; sodium triethylborohydride In hexane at 70℃; Inert atmosphere; Sealed tube; chemoselective reaction; | |
| 68 % | With 3,3'-bis[(diphenylphosphino)methyl]-2,2'-bipyridine; cobalt(II) aceylacetonate In ethyl acetate at 25℃; Schlenk technique; | |
| 83 % | With C38H30ClNOP2Pt In tetrahydrofuran at 50℃; Inert atmosphere; Schlenk technique; stereoselective reaction; |

| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 65% | With copper(I) oxide In 1,4-dioxane at 100℃; 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 |
|---|---|---|
| With C178H184ClCuN2O33; potassium <i>tert</i>-butylate In tetrahydrofuran; methanol at 20℃; for 16h; Inert atmosphere; regioselective reaction; |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 99% | 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. |
| 95% | With triphenylphosphine In ethanol at 50℃; for 2h; | |
| 86% | With copper(I) oxide; triphenylphosphine In 1,4-dioxane at 60℃; for 5h; |
| 83% | With [Cu(phen)(xantphosTEPD)]PF6; potassium carbonate In water; acetonitrile at 20℃; for 7h; Sealed tube; Inert atmosphere; Irradiation; diastereoselective reaction; | |
| 83% | With copper on metal organic framework OH-HKUST-1 heterogeneous catalyst In methanol at 25℃; for 8h; Inert atmosphere; Schlenk technique; | 6 Example 6: Preparation of (E)-vinyl borate by 3-chloro-1-ethynylbenzene and B2Pin2 catalyzed by heterogeneous catalyst OH-HKUST-1-15% The heterogeneous catalyst OH-HKUST-1-15% (0.015 mmol), B2Pin2 (2 mmol), 3-chloro-1-ethynylbenzene (0.5 mmol), and anhydrous methanol (1 mL) were added sequentially to a 5 mL Schlenk reaction tube equipped with a magnetic stirrer. The reaction tube was evacuated and filled with nitrogen gas having a volume concentration of 99.99% through a double-row tube, and the process was repeated three times. The reaction tube containing the reaction mixture was then subjected to magnetic stirring for reaction at 25° C. for 8 h. After the reaction, the solid catalyst was removed by filtration. The filtrate was purified by silica gel column chromatography (eluted with a mixture of petroleum ether and ethyl acetate in a volume ratio of 50:1). The eluate was collected and dried by rotary evaporation at 40° C. to obtain the (E)-vinyl borate product. The product yield was determined to be 83% by 1H NMR analysis, and the selectivity was 99.1%. |
| 80% | With potassium carbonate; 6Cu(1+)*3C20H14N6O4(2-) In water; acetonitrile at 25℃; for 0.333333h; stereoselective reaction; | |
| 80% | With water; potassium carbonate; 6Cu(1+)*3C20H14N6O4(2-) In acetonitrile at 25℃; for 0.333333h; stereoselective reaction; | |
| Stage #1: bis(pinacol)diborane With copper; sodium methylate In 1,4-dioxane; ethanol for 0.5h; Inert atmosphere; Sealed tube; Stage #2: m-chlorophenylacetylene In 1,4-dioxane; ethanol at 60℃; Inert atmosphere; | ||
| Stage #1: bis(pinacol)diborane With copper; sodium methylate In 1,4-dioxane; ethanol for 0.5h; Inert atmosphere; Schlenk technique; Stage #2: m-chlorophenylacetylene In 1,4-dioxane; ethanol at 60℃; for 12h; Inert atmosphere; Schlenk technique; | ||
| 57 % | Stage #1: bis(pinacol)diborane With Xantphos; copper(l) chloride; sodium t-butanolate In tetrahydrofuran Schlenk technique; Inert atmosphere; Stage #2: m-chlorophenylacetylene In tetrahydrofuran; methanol at 20℃; Schlenk technique; Inert atmosphere; | 47 Synthesis of (E)-2-(3-chlorostyryl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane CuCl (287 mg, 2.9 mmol), t-BuONa (557 mg, 5.8 mmol), and Xantphos (1.7 g, 2.9 mmol) were placed in an oven-dried Schlenk tube under nitrogen and THF (60 mL) was added. The reaction mixture was stirred for 30 min at room temperature and then bis(pinacolato)diboron (7.4 g, 29 mmol) in THF (30 mL) was added. The reaction mixture was stirred for 10 min and 1-chloro-3-ethynylbenzene (4 g, 29 mmol) was added, followed by MeOH (1.8 g, 58 mmol). The mixture was stirred at room temperature for 18h. After completed, the reaction mixture was quenched with water (80 mL), extracted with EtOAc (80 mL x 3). The combined organic layers were washed with brine (80 mL), dried over anhydrous Na2SO4, filtered and concentrated in vacuo. The reside was purified by column chromatography on silica gel (eluent: EtOAc/PE = 0 - 3%) to afford (E)-2-(3-chlorostyryl)-4,4,5,5- tetramethyl-1,3,2-dioxaborolane (4.4 g, 57%) as pale-yellow sticky oil. ESI-MS [M + H] +: 265.1. |
| 89 % | With ethanol at 30℃; Autoclave; Inert atmosphere; | |
| 81 % | With methanol; N-propyl-N-(2-(pyridin-2-ylamino)phenyl)formamide In tetrahydrofuran at 60℃; Schlenk technique; stereoselective reaction; | |
| 78 % | With aluminum oxide; copper(II) acetate hydrate; triphenylphosphine In tetrahydrofuran; methanol at 20℃; | General procedure B General procedure: The mixture of alkyne (0.3 mmol, 1 equiv.), B2Pin2 (91.5 mg, 0.36 mmol,1.2 equiv.), Cu(OAc)2H2O (3 mg, 0.015 mmol, 5% mol), PPh3 (7.8 mg,0.03 mmol, 10% mol), Al2O3 (abcr AB354683, 37.5 mg, 0.36 mmol, 1.2equiv.), and MeOH (24.3 μL, 2 equiv.) was stirred in THF (1.5 ml) atambient temperature for 4 h under Ar atmosphere. Then the mixturewas diluted with CH2Cl2, filtered through celite, and evaporated in vacuo.The crude product was purified by column chromatography. |

| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 94% | With bis(cyclopentadienyl)dihydrozirconium In toluene at 25℃; Inert atmosphere; Glovebox; | |
| 51% | With tetrakis(trimethylphosphine)iron(0); norbornene In hexane at 50℃; for 18h; stereoselective reaction; | |
| 50 % | With potassium hexamethylsilazane; C18H14BrMnN2O3S In tetrahydrofuran at 65℃; Inert atmosphere; Green chemistry; chemoselective reaction; |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| Stage #1: (E)-2-(3-chlorostyryl)-4,4,5,5-tetramethyl-1,3-dioxa-2-borolane With sodium periodate In tetrahydrofuran; water for 0.5h; Stage #2: With hydrogenchloride In tetrahydrofuran; water at 20℃; | ||
| Stage #1: (E)-2-(3-chlorostyryl)-4,4,5,5-tetramethyl-1,3-dioxa-2-borolane With sodium periodate In tetrahydrofuran; water at 20℃; for 0.5h; Inert atmosphere; Stage #2: With hydrogenchloride In tetrahydrofuran; water at 20℃; for 17h; Inert atmosphere; |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| Multi-step reaction with 2 steps 1.1: sodium periodate / tetrahydrofuran; water / 0.5 h 1.2: 20 °C 2.1: potassium phosphate / toluene / 12 h / 60 °C |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| Multi-step reaction with 2 steps 1.1: sodium periodate / tetrahydrofuran; water / 0.5 h 1.2: 20 °C 2.1: potassium phosphate / toluene / 12 h / 60 °C |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| Multi-step reaction with 2 steps 1.1: sodium periodate / tetrahydrofuran; water / 0.5 h 1.2: 20 °C 2.1: potassium phosphate / toluene / 12 h / 60 °C |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 79% | With 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; copper(I) thiocyanate; CyJohnPhos; lithium tert-butoxide In 1,2-dichloro-ethane at 80℃; for 24h; Inert atmosphere; Schlenk technique; Sealed tube; regioselective reaction; |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| Multi-step reaction with 2 steps 1: bis(cyclopentadienyl)dihydrozirconium / toluene / 25 °C / Inert atmosphere; Glovebox 2: bis(cyclopentadienyl)dihydrozirconium / toluene / 130 °C / Inert atmosphere; Glovebox |
| Yield | Reaction Conditions | Operation in experiment |
|---|---|---|
| 79 %Chromat. | With bis(cyclopentadienyl)dihydrozirconium In toluene at 130℃; Inert atmosphere; Glovebox; |