Abstract: Commercially available and inexpensive potassium bis(trimethylsilyl)amide (KHMDS) serves as an efficient transition metal-free catalyst for the catalytic sp C?H silylation of several terminal alkynes including two pharmaceuticals. Overall, the presented system allows the synthesis of various attractive silylacetylenes under mild conditions, making this approach an environmentally benign and sustainable alternative to existing synthetic solutions.
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With indium(III) triflate; water; toluene-4-sulfonic acid; In 1,2-dichloro-ethane; for 4h;Sealed tube; Reflux;
General procedure: The reaction mixture of In(OTf)3 (11.2 mg, 2 mol %), PTSA (57.1 mg, 30 mol %), DCE (2.0 mL), alkynes 1a-1n or 1p-1t (1.0 mmol) and water (0.2 mL) in a 10 mL flask or in a 10 mL sealed tube was stirred at reflux and monitored periodically by TLC. Upon completion, DCE was removed under reduced pressure using an aspirator, and then the residue was purified by flash chromatography (PE/EA) on silica gel to afford corresponding carbonyl compounds 2a-2n or 2p-2t.
91%
With C20H14AuN2O2(1+)*Cl(1-); water; trifluoroacetic acid; In methanol; at 80℃; for 5h;Sealed tube;
General procedure: Alkyne (0.5 mmol), catalyst (2.0 mol%), H2O (4.0 equiv., 0.04 mL) and CF3COOH (2.0 mol%) were dissolvedin MeOH (0.4 mL) and the homogeneous solution was stirred in a sealed tube at 80C for 5 h. After the completion of the reaction, the mixture was cooled to room temperature, and then CH2Cl2 and H2O were added to it. The organic layer was separated and washed with brine, dried over Na2SO4, and concentrated under reduced pressure. The residue was purified over silica gel by column chromatography (25% EtOAc in hexane).
89%
With chloro(1,3-bis(2,6-di-i-propylphenyl)imidazol-2-ylidene)gold(I); water; In methanol; at 110℃; for 6h;
The catalyst [(IPr) AuCl] (3.1mg, 0.5mol%), 4- propylbenzene acetylene (1mmol), in methanol (1ml) and water (0.5ml) was added successively 25ml reactor.After the reaction mixture was reacted for 6 hours at 110 , cooled to room temperature.Rotary evaporation to remove the solvent, then purified by column chromatography (eluent: petroleum ether / ethyl acetate) to give pure title compound, yield: 89%
88%
With Perfluorooctanesulfonic acid; C8AgF17O3S*H2O; In water; at 100℃; for 8h;Darkness;
General procedure: To the mixture of phenylacetylene (1 mmol), water (3.0 mL),silver perfluorooctanesulfonate (5 mol%) and perfluorooctane sulfonateacid (2 mol%) was added. The mixture was stirred at 100 Cfor 8 h. The solution was extracted with n-hexane (diethyl ether)(3 5 mL), the combined extract was dried with anhydrous MgSO4. The rest of the solution was used for the next cycle of reaction. Theextraction solvent was removed and the crude product was separatedby column chromatography to give the pure sample.
With chloro(1,3-bis(2,6-di-i-propylphenyl)imidazol-2-ylidene)gold(I); water; silver trifluoromethanesulfonate; In methanol; at 120℃; for 6h;
The 4-propylphenylacetylene (144 mg, 1.0 mmol), cat. [Au] (6 mg, 1 μM %), AgOTf (2.6 mg, 1 μM %), water (36 mg, 2 mmol) and methanol (1 ml) are added to the 25 mL of Claisen tube or. After closing the reaction at 120 C for 6 hours, cooling to room temperature. Then adding formic acid amine (315 mg, 5 mmol) and cat. [Rh] (6.2 mg, 1 mmol %), the reaction mixture in oil bath heated to 80 C, reaction 12 hours, cooling to room temperature. Rotary evaporation of the solvent and add a certain amount of ethyl acetate and water extraction, the organic phase of the resulting product after concentrated hydrochloric acid the reflex process, rotary evaporation to remove the solvent, the final petroleum ether washing and filtering to obtain the pure target compound, yield: 85%
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