| 100% |
With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; N,N-diisopropylamine In tetrahydrofuran at 20℃; for 5h; Inert atmosphere; |
1-Bromo-2-[2-(trimethylsilyl)ethynyl]-benzene (11)
Toa solution of 1-bromo-2-iodobenzene (10, 1.0 mL, 8.0 mmol) in THF (50 mL) were added PdCl2(PPh3)2 (112 mg, 0.16 mmol), CuI (15 mg, 0.080 mmol), trimethylsilylacetylene (1.4 mL, 8.8 mmol) and iPr2NH (7.8 mL, 56 mmol) at room temperature. After being stirred for 5 h, the mixture was quenched by addition of saturated aqueous NH4Cl and extracted with hexane. The extract was washed with water and brine, dried and concentrated to dryness. The residue was chromatographed with hexane to give 11 (2.28 g, quantitative yield) as a pale yellow oil: 1H-NMR (400 MHz, CDCl3) δ: 7.61 (d, 1H, J=8.1 Hz), 7.53 (dd, 1H, J=7.8, 1.4 Hz), 7.28 (dd, 1H, J=7.8, 7.8 Hz), 7.19 (dd,1H, J=8.1, 7.8 Hz), 0.32 (s, 9H). NMR data is identical to literaturedata.36) |
| 100% |
With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; triethylamine at 20℃; for 19h; Inert atmosphere; Schlenk technique; Glovebox; |
|
| 99% |
With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; triethylamine In tetrahydrofuran at 20℃; Inert atmosphere; |
|
| 99% |
With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; triethylamine In tetrahydrofuran at 20℃; Inert atmosphere; |
|
| 99% |
With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; triethylamine at 20℃; for 3h; Inert atmosphere; |
|
| 99% |
With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; triethylamine at 65℃; for 16h; |
|
| 99% |
With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; triethylamine for 65h; Inert atmosphere; |
1-[Dimethyl(thexyl)silyl]ethynyl}-2-ethynylbenzene (7) from 1-Bromo-2-iodobenzene
Under N2, 1-bromo-2-iodobenzene (30.0 g, 106 mmol) was added to astirred solution of Pd(PPh3)2Cl2 (149.0 mg, 0.21 mmol) and CuI (16.2mg, 0.085 mmol) in Et3N (300 mL). (Trimethylsilyl)ethyne (10, 22.5mL, 15.5 g, 158 mmol) was injected and the mixture stirred for 65 h.The volatiles were removed in vacuo and the remaining residue dissolved in Et2O (100 mL), which was washed with aq 2 M HCl (3 × 30mL), then H2O (30 mL), and dried (MgSO4). Evaporation of the solvent gave a brown-orange oil, which was subjected to column chromatography (silica gel, hexanes) to give 1-bromo-2-[(trimethylsi-lyl)ethynyl]benzene (26.7 g, 99%) as a yellow-orange oil. |
| 99% |
With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; triethylamine at 20℃; for 3h; Inert atmosphere; |
|
| 99% |
With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; triethylamine Inert atmosphere; Schlenk technique; |
|
| 99% |
With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; triethylamine In tetrahydrofuran at 20℃; Inert atmosphere; |
1.1 Preparation of Compound 1-1
Under a nitrogen condition of l-bromo-2-iodobenzene(1-bromo-2-iodobenzene) (5.66g, 20 m) to THF (15) and triethylamine Dissolved in (Triethylamine) (15).Trimethylsilane (Ethynyltrimethylsilane) (2.16g, 20m) ethynyl, Insert thePdCl2 (PPh3) 2 (70, 0.5%), CuI (38, 1%) was stirred at room temperature.After completion of the reaction by diluting with diethyl Le (diethylether) iswashed with brine (brine) using Na2SO4 and purified by silica gel (silica gel)and then through a process of concentration to remove the moisture. To give thetitle compound 5g (yield> 99%). |
| 99% |
With copper (I) iodide; palladium diacetate; triethylamine; triphenylphosphine at 20℃; for 11h; Inert atmosphere; |
|
| 99% |
With palladium (II) [1,1'-bis(diphenylphosphanyl)ferrocene] dichloride; copper (I) iodide; triethylamine at 20℃; for 12h; Inert atmosphere; |
1.1 1st step, compound 1 of synthesis
N2Atmosphere, in the reaction tube to join the neighbouring iodine bromophenylacetic (4.000 g, 14 . 139 mmol), three a radical silicon acetylene (1.528 g, 15 . 553 mmol) and catalyst Pd (PPh3)2Cl2(99 Mg, 0 . 141 mmol, 1% mol), CuI (54 mg, 0 . 283 mmol, 2% mol), then add 50 ml triethylamine, react at room temperature for 12 h. After the reaction is complete filtering and washing three times with petroleum ether, the combined organic solution and concentrated. The crude product with silica gel column purification, eluting agent is petroleum ether, the final product is a yellow liquid 3.527 g, yield 99%. |
| 99% |
With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; triethylamine at 20℃; Inert atmosphere; |
|
| 99% |
With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; triethylamine at 20℃; for 5h; Schlenk technique; Inert atmosphere; |
|
| 98% |
With ammonia hydrochloride; triethylamine In lithium hydroxide monohydrate at 20℃; for 1h; |
|
| 98% |
With copper (I) iodide; triethylamine at 20℃; |
|
| 98% |
With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; triethylamine at 20℃; Inert atmosphere; |
|
| 97% |
With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; triethylamine In tetrahydrofuran for 4h; Reflux; |
|
| 96% |
With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; triethylamine In tetrahydrofuran at 20℃; for 2.16667h; Reflux; Inert atmosphere; |
|
| 96% |
With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide In triethylamine at 23℃; for 21h; Inert atmosphere; Schlenk technique; |
|
| 96% |
Stage #1: 1-Bromo-2-iodobenzene With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; triethylamine for 0.25h; Inert atmosphere; Schlenk technique;
Stage #2: trimethylsilylacetylene at 20℃; for 15h; Inert atmosphere; Schlenk technique; |
|
| 95% |
Stage #1: 1-Bromo-2-iodobenzene With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; N,N-diisopropylamine for 0.5h; Inert atmosphere;
Stage #2: trimethylsilylacetylene at 25℃; for 5h; Inert atmosphere; |
|
| 95% |
With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; triethylamine at 20℃; Inert atmosphere; Sealed tube; |
|
| 95% |
With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; triethylamine In tetrahydrofuran at 20℃; |
|
| 95% |
With copper (I) iodide; tetrakis-(triphenylphosphine)-palladium; triethylamine Inert atmosphere; |
|
| 94% |
With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; diethylamine at 0℃; |
|
| 94% |
Stage #1: 1-Bromo-2-iodobenzene With copper (I) iodide; tetrakis-(triphenylphosphine)-palladium; triethylamine In tetrahydrofuran for 0.166667h; Schlenk technique; Inert atmosphere;
Stage #2: trimethylsilylacetylene In tetrahydrofuran at 21℃; for 96h; Schlenk technique; Inert atmosphere; Sealed tube; chemoselective reaction; |
|
| 93% |
With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; triethylamine |
|
| 93% |
With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; triethylamine |
|
| 92% |
With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide at 20℃; for 23h; |
|
| 92% |
With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; diethylamine In tetrahydrofuran at 20℃; for 12h; Inert atmosphere; |
1-(Methoxydimethylsilyl)-2-[2-(trimethylsilyl)ethynyl]benzene (5a)
Under argon atmosphere, PdCl2(PPh3)2 (0.25 g, 0.35 mmol) and CuI (0.067 g, 0.35 mmol) were placed in a two-necked flask. Et2NH (20 mL) and THF (20 mL) were successively added to the flask. 1-Bromo-2-iodobenzene (2.21 mL g, 17.7 mmol) and trimethylsilylacetylene (2.93 mL, 21.2 mmol) were successively added to the mixture. The mixture was stirred at room temperature for 12 h and then evaporated. The residue was diluted with hexane/AcOEt (5:1) and washed with 1 M aqueous HCl. The organic layer was dried over Na2SO4 and concentrated under reduced pressure. Purification of the residue by silica-gel column (hexane) gave 1-bromo-2-[2-(trimethylsilyl)ethynyl]benzene [38274-16-7] as a pale yellow clear liquid (4.12 g, 16.3 mmol, 92% yield). Under argon atmosphere, n-BuLi (2.65 M in hexane, 701 mL, 1.86 mmol) was added to a stirred solution of 1-bromo-2-[2-(trimethylsilyl)ethynyl]benzene (472 mg, 1.86 mmol) in THF (4 mL) at -78 °C. After 0.5 h, Me2SiCl2 (223 mL, 1.86 mmol) was added to the mixture at that temperature. Then the mixture was allowed to warm to room temperature and stirred for 2 h. MeOH (0.5 mL) and Et3N (290 mL, 2.08 mmol) were successively added to the reaction mixture at -78 °C. The resultant mixture was stirred at room temperature for 1 h. The mixture was quenched with water and extracted three times with hexane/AcOEt (30:1). The combined organic layer was dried over Na2SO4 and evaporated. The residue was purified by flash column chromatography (hexane/AcOEt= 40:1). 1-(Methoxydimethylsilyl)-2-[2-(trimethylsilyl)ethynyl]benzene (5a) was obtained as a pale yellow liquid (0.721 g, 2.75 mmol, 71% yield). |
| 92.9% |
With copper (I) iodide; tetrakis-(triphenylphosphine)-palladium; triethylamine at 20 - 25℃; for 48h; Inert atmosphere; |
1.A Preparation of intermediate a
Under nitrogen protection, o-bromoiodobenzene (42.4 g, 0.15 mol) and trimethylsilylacetylene (17.7 g, 0.18 mol) were dissolved in 250 mL of triethylamine in a 500 mL three-Finally, tetrakis (triphenylphosphine) palladium (5.1g, 4.5mmol) and cuprous iodide (1.71g, 9mmo 1) were added and the reaction was carried out at the temperature of 20-25 ° C under stirring for 48 hours. The reaction formula is as follows: After the reaction is completed, 500 mL of water is poured into the reaction system to quench the reaction, 200 mL of toluene is added to extract the product, and the product is washed with deionized water, Crystallization from petroleum ether / ethanol gave the white solid as an intermediate a. The yield was 92.9%. |
| 92% |
With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; diethylamine In tetrahydrofuran at 20℃; for 12h; Inert atmosphere; |
4.1.1. Synthesis of methoxysilanes 1 (typical procedure)
General procedure: Et2NH (20 mL), THF (20 mL), 1-bromo-2-iodobenzene (2.2 mL g,18 mmol), and trimethylsilylacetylene (2.9 mL, 21 mmol) weresuccessively added to a flask containing PdCl2(PPh3)2 (0.25 g,0.35 mmol) and CuI (0.067 g, 0.35 mmol). The mixture was stirredat room temperature for 12 h and then evaporated. The residuewasdiluted with hexane/AcOEt (5:1) and washed with 1M aqueousHCl. The organic layer was dried over Na2SO4 and evaporated. Purificationof the residue by silica-gel column (hexane) gave 1-bromo-2-[2-(trimethylsilyl)ethynyl]benzene [38274-16-7] (1a’) asa pale yellow clear liquid (4.12 g, 16.3 mmol, 92% yield).nBuLi (2.65M in hexane, 701 mL, 1.86 mmol) was added to astirred solution of 1a’ (472 mg, 1.86 mmol) in THF (4 mL) at 78 C.After 0.5 h, Me2SiCl2 (223 mL, 1.86 mmol) was added to the mixtureat that temperature. Then the mixture was warmed to room temperatureand stirred for 2 h. MeOH (0.5 mL) and Et3N (290 mL,2.08 mmol) were successively added to the reaction mixtureat 78 C. After removing the cooling bath, the resultant mixturewas stirred at room temperature for 1 h. The mixturewas quenchedwith water and extracted with hexane/AcOEt (30:1) three times.The combined organic layer was dried over Na2SO4 and evaporated.The residuewas purified by flash column chromatography (hexane/AcOEt 40:1). The title compound,1-(methoxydimethylsilyl)-2-[2-(trimethylsilyl)ethynyl]benzene (1a), was obtained as a pale yellowliquid (0.721 g, 2.75 mmol, 71% yield). 1H NMR (500 MHz, CDCl3,7.26 ppm) d 0.25 (s, 9H), 0.47 (s, 6H), 3.56 (s, 3H), 7.30e7.34 (m, 2H),7.48e7.50 (m, 1H), 7.59e7.61 (m, 1H); 13C NMR (125 MHz, CDCl3,77.0 ppm) d 1.8, 0.3, 50.9, 96.9, 106.4, 127.7, 127.7, 129.2, 132.8,134.0, 140.8; IR (neat) 3073, 3052, 2959, 2831, 2155, 1429 cm1;HRMS (EI) calcd for C14H22OSi2 [M] 262.1209, found 262.1209.The substrates 1b-l, and 1p were synthesized by the samemanner as described for the preparation of 1a. |
| 92% |
With piperidine; [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide In toluene at 45℃; for 4h; |
|
| 92% |
With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; triethylamine In tetrahydrofuran at 20℃; Inert atmosphere; |
|
| 91% |
With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; diethylamine for 3.5h; Ambient temperature; |
|
| 91% |
With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide In triethylamine at 20℃; for 24h; |
|
| 91% |
With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; triethylamine In tetrahydrofuran at 20℃; for 1h; Inert atmosphere; chemoselective reaction; |
|
| 90% |
With copper (I) iodide; 2,2'-iminobis[ethanol] In tetrahydrofuran at 55℃; for 15h; |
|
| 90% |
With 1,2-bis(thiophen-2-ylethynyl)benzene; [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); triethylamine In acetonitrile at 60℃; for 17h; Inert atmosphere; |
|
| 90% |
With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; trimethylamine for 0.5h; Inert atmosphere; Schlenk technique; Reflux; |
|
| 90% |
With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; triethylamine at 20℃; for 3h; Inert atmosphere; |
|
| 89% |
With copper (I) iodide; trans-bis(triphenylphosphine)palladium(II) chloride; triethylamine at 25℃; for 12h; |
|
| 89% |
With triethylamine |
|
| 89% |
With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; diethylamine for 12h; |
|
| 89% |
With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; triethylamine at 20℃; for 23h; Inert atmosphere; |
|
| 88% |
With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; triethylamine at 20℃; Inert atmosphere; |
|
| 88% |
With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; triethylamine In tetrahydrofuran at 20℃; for 6h; Inert atmosphere; |
|
| 88% |
With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; triethylamine In tetrahydrofuran at 20℃; for 72h; Schlenk technique; Inert atmosphere; |
|
| 87% |
With copper (I) iodide; triethylamine for 68h; Ambient temperature; |
|
| 86% |
With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; diethylamine at 20℃; for 10h; Inert atmosphere; |
|
| 86% |
With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; diethylamine for 10h; Inert atmosphere; |
|
| 84% |
With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; triethylamine In tetrahydrofuran at 0 - 20℃; Inert atmosphere; |
|
| 84% |
With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; triethylamine at 25℃; for 5h; Inert atmosphere; |
|
| 84% |
With copper (I) iodide; trans-bis(triphenylphosphine)palladium(II) dichloride; triethylamine Inert atmosphere; Schlenk technique; |
|
| 82% |
With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; triethylamine In tetrahydrofuran at 20℃; for 24h; Inert atmosphere; |
|
| 82% |
With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; triethylamine In tetrahydrofuran at 20℃; for 24h; Inert atmosphere; Reflux; |
Compound 133:
A 50mL round bottomfiask equipped with a magnetic stir bar was charged with compound 132(35 mmol),THF (100 mL), triethylamine (20 mL, l5Ommol), PdCI2(PPh3)2 (500 mg, 0.7mmol),Cul (150mg, 0.754 mmol) and trimethylsilylacetylene (5.25 mL, 37.lmmol) under argon atmosphere. The reaction mixture was stirred overnight at room temperature, diluted in CH2CI2, washed with NH4CI and dried over Mg2SO4. The solvent was removed under reduced pressure and the crude product was purified by flash chromatography on silica gel with hexanes as elu10 ent to afford the desired compound 133 (1 33a: 82%, 1 33b: 85%) as yellow orange oil.133a: 1H-NMR (CD2CI2, 250 MHz): 7.58 (d, 1H), 7.49 (dd,1H), 7.24 (t, 1H), 7.16 (t, 1H), 0.28 (s,9H);133b: 1H-NMR (CD2CI2, 250 MHz): 7.48 (s, 1H), 7.32 (dd,1H), 7.18 (dd, 1H), 1.6 (s, 9H), 0.28 (s,9H); |
| 81% |
With copper (I) iodide; tetrakis-(triphenylphosphine)-palladium; triethylamine at 0 - 45℃; Inert atmosphere; Schlenk technique; |
|
| 80% |
With piperidine; [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide In benzene at 80 - 90℃; for 12.5h; |
|
| 79% |
With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; triethylamine In N,N-dimethyl-formamide at 50℃; for 6h; Inert atmosphere; |
|
| 78% |
With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; diethylamine for 18h; Inert atmosphere; |
|
| 75% |
With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; triethylamine at 20℃; for 3h; |
|
| 75% |
With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; triethylamine In tetrahydrofuran at 23℃; for 1h; Inert atmosphere; Schlenk technique; |
|
| 74% |
With copper (I) iodide; tetrakis-(triphenylphosphine)-palladium; N,N-diisopropylamine In tetrahydrofuran at -15 - 25℃; for 16h; Inert atmosphere; |
|
| 74% |
With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; triethylamine at 20℃; for 12h; Inert atmosphere; |
|
| 60% |
With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; triethylamine In tetrahydrofuran at 20℃; for 12h; Inert atmosphere; |
|
|
With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; triethylamine at 50℃; |
|
|
With copper (I) iodide; triethylamine at 20℃; for 4h; |
|
|
With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; triethylamine at 20℃; Inert atmosphere; |
|
|
With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; triethylamine at 20℃; Inert atmosphere; |
|
|
With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; triethylamine In tetrahydrofuran at 0 - 20℃; |
|
|
With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide In tetrahydrofuran; triethylamine at 20℃; |
|
|
With copper (I) iodide; trans-bis(triphenylphosphine)palladium(II) dichloride; triethylamine for 24h; Inert atmosphere; |
|
|
With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; diethylamine at 20℃; for 18h; Inert atmosphere; |
|
|
Inert atmosphere; |
|
|
With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide In triethylamine at 20℃; for 3.5h; |
|
|
With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; triethylamine at 25℃; |
|
|
With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; triethylamine In tetrahydrofuran |
|
|
With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; triethylamine at 60℃; for 12h; Inert atmosphere; |
|
|
With copper (I) iodide; tetrakis-(triphenylphosphine)-palladium at 20℃; Inert atmosphere; |
|
|
Stage #1: 1-Bromo-2-iodobenzene With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide In diethylamine at 20℃; for 0.0833333h;
Stage #2: trimethylsilylacetylene In diethylamine at 20℃; for 12h; |
|
|
With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; triethylamine In tetrahydrofuran at 20℃; for 2h; |
|
|
With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; triethylamine In tetrahydrofuran at 40℃; Inert atmosphere; Schlenk technique; |
|
|
With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide |
|
|
With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; diethylamine at 20℃; Inert atmosphere; |
|
|
With palladium (II) [1,1'-bis(diphenylphosphanyl)ferrocene] dichloride; copper (I) iodide; triethylamine In tetrahydrofuran |
|
| 1.51 g |
With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; triethylamine at 20℃; Inert atmosphere; Sealed tube; |
|
|
Stage #1: 1-Bromo-2-iodobenzene With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; triethylamine In tetrahydrofuran for 0.166667h; Inert atmosphere;
Stage #2: trimethylsilylacetylene In tetrahydrofuran for 12h; Inert atmosphere; |
|
|
Stage #1: 1-Bromo-2-iodobenzene With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide for 0.166667h;
Stage #2: trimethylsilylacetylene for 18h; |
|
|
With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; triethylamine at 20℃; for 3h; |
|
|
With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; triethylamine at 50℃; for 8h; Inert atmosphere; |
General procedure A:
General procedure: To a three-necked flask charged with a magnetic stirring bar was added 1-bromo-2-iodobenzene (15 mmol), ethynyltrimethylsilane (15 mmol), Pd(PPh3)2Cl2 (2 mol %), CuI (1 mol %) in triethylamine (50 mL) under nitrogen. The mixture wasstirred at 50 °C for 8 hours. the solvent was removed by rotary evaporation. The residue was treated with water and extracted with dichloromethane. The combined organic layer was concentrated under reduced pressure. The crude product was purified flash column chromatography on silica gel using petroleum ether as an eluent.To a solution of trimethyl(phenylethynyl)silane (10 mmol) in methanol (15 mL) and THF (15 mL) was added K2CO3 (4 equiv.) and stirred at rt for 6 hours. The resulting mixture was treated with water and extracted with ethyl ether. The combined organic layer dried over anhydrous Na2SO4. The solvent was removed and the residue was purified by silica gel column chromatography to afford the pure product 1a2 in 85 % yield. Substrates1b2 and 1c were also prepared following the general procedure A. |
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With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; diethylamine In N,N-dimethyl-formamide at 50℃; for 24h; Inert atmosphere; |
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Stage #1: 1-Bromo-2-iodobenzene With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; triethylamine at 20℃; for 0.5h; Schlenk technique; Inert atmosphere;
Stage #2: trimethylsilylacetylene at 20℃; for 4h; Schlenk technique; Inert atmosphere; |
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With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; triethylamine at 20℃; Inert atmosphere; Schlenk technique; |
General Procedure 1 for the Synthesis of Terminal Alkynes 16a-16c, 20, and 39 (Sonogashira Coupling-Desilylation)
General procedure: The respective 2-iodobenzene was dissolved in Et3N (0.2 M) in a dry round-bottom flask (RBF), followed by addition of CuI (4-6 mol-%) and Pd(PPh3)2Cl2 (2-3 mol-%). The RBF was then degassed and backfilled with N2 three times. Finally, trimethylsilylacetylene (1.2 equiv.) was added dropwise under an N2 atmosphere. The reaction mixture was stirred at rt overnight. On completion, the suspension was filtered through Celite and extracted with Et2O twice, and washed with H2O twice and with brine twice; the combined organic extracts were dried over anhydrous MgSO4, filtered, and concentrated under reduced pressure. The crude product was purified by a silica plug (100% hexanes) to yield the TMS-protected terminal alkyne, which was then dissolved in MeOH/Et2O (2 : 1, 0.2 M), followed by addition of K2CO3 (1.5 equiv.). The reaction mixture was stirred at rt overnight. On completion, the mixture was concentrated to a residue and taken up in Et2O. Washed with H2O twice and with brine twice, the organic extract was dried over anhydrous MgSO4, filtered, and concentrated to yield the desired terminal alkynes, which were directly used in the next step without further purification. |
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Stage #1: 1-Bromo-2-iodobenzene With copper (I) iodide; tetrakis-(triphenylphosphine)-palladium; N,N-diisopropylamine In toluene at 20℃; for 0.25h; Inert atmosphere;
Stage #2: trimethylsilylacetylene In toluene at 80℃; Inert atmosphere; |
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With [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II); copper (I) iodide; triethylamine at 20℃; Inert atmosphere; |
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