3,3-dimethylbut-1-ynylbenzene

Conditions: temp:60.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A solution containing W(CCMe3)(Cl3)(OPEt3) (0.43 g, 0.866 mmol) and diphenylacetylene (0.18 g, 1.0 mmol) in 2 ml of tetrahydrofuran was heated to 60° C. for 2 hours. During this time, the color of the reaction mixture changed from blue to green. Phenyl-t-butylacetylene (100% yield versus tungsten) was observed in the reaction mixture by gas chromatography. The reaction mixture was filtered and PMe3 (0.30 ml, 3.0 mmol) was added by syringe. The color of the solution turned yellow, and after the addition of 2 ml pentane, yellow crystals precipitated from solution. The product was collected by filtration and was recrystallized from a mixture of tetrahydrofuran and pentane at -30° C.; total yield 0.47 g (89%) W(CPh)Cl3 (PMe3)3.

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A solution of (3,3-Dimethylbut-1-ynyl)benzene (400 mg, 2.53 mmol) and dimethyl nitromalonate (0.853 mL, 6.32 mmol) in mesitylene (5 mL) was heated at 150° C. for 48 h. The reaction mixture was concentrated, and the residue was purified by silica gel chromatography with hexanes/ethyl acetate (10/1) to yield methyl 4-tert-butyl-5-phenylisoxazole-3-carboxylate (101 mg). The compound had an HPLC ret. time=3.39 min.−Column. YMC S5 COMBISCREEN® 4.6×50 mm; Gradient time: 4 min; Flow rate=4 ml/min; Solvent A=10% MeOH−90% Water−0.2% H3PO4; Solvent B=90% MeOH−10% water−0.2% H3PO4; Start % B=0; Final % B=100. LC-MS: M+1=260+. The reaction mixture was concentrated the residue was purified by silica gel chromatography with hexanes/ethyl acetate (10/1)

Conditions: temp:75.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A degassed solution of iodobenzene (0.549 mL, 4.90 mmol), dichlorobis(triphenylphosphine)-palladium(II) (0.206 g, 0.294 mmol), copper(I) iodide (0.047 g, 0.245 mmol), and diisopropylamine (3.49 mL, 24.5 mmol) in N,N-dimethylformamide (20 mL) was added 3,3-dimethylbut-1-yne (0.896 mL, 7.35 mmol). The reaction mixture was and heated to 75° C. for 45 minutes. The reaction mixture was then diluted with ethyl acetate (150 mL), washed with 10% aqueous solution of lithium chloride (2×100 mL), washed with a 2M aqueous solution of ammonium hydroxide, washed with brine (100 mL), and dried over anhydrous sodium sulfate. Concentration followed by purification on silica gel chromatography with hexanes/dichloromethane (10/1) afforded (3,3-Dimethylbut-1-ynyl)benzene (740 mg). The compound had an HPLC ret. time=3.78 min.−Column: YMC S5 COMBISCREEN® 4.6×50 mm; Gradient time: 4 min; Flow rate=4 ml/min; Solvent A=10% MeOH−90% Water−0.2% H3PO4; Solvent B=90% MeOH−10% water−0.2% H3PO4; Start % B=0; Final % B=100. washed with 10% aqueous solution of lithium chloride (2×100 mL) washed with a 2M aqueous solution of ammonium hydroxide washed with brine (100 mL) dried over anhydrous sodium sulfate Concentration followed by purification on silica gel chromatography with hexanes/dichloromethane (10/1)