2-methyl-N-propan-2-ylidenepropane-2-sulfinamide

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A solution of n-butyllithium in hexanes (1.65 M, 5.2 mL) was added dropwise to a solution of 4-bromo-N,N-bis(trimethylsilyl)aniline (2.55 mL) in THF (14 mL) at −78° C. The resulting mixture was stirred for 1.5 h at −78° C. before a solution of N-isopropylidene-2-methylpropane-2-sulfinamide in THF (2.8 mL) was added dropwise at −78° C. The reaction mixture was stirred for an additional 1 h at −78° C. then allowed to warm to room temperature. After being stirred for 18 h at room temperature, the reaction mixture was poured into ice cooled saturated sodium bicarbonate solution. The aqueous layer was extracted with ethyl acetate. The combined organic layer was washed with saturated sodium bicarbonate solution and brine and then dried over anhydrous sodium sulfate. The dried solution was filtered and the filtrate was concentrated to dryness. The residue was diluted with diisopropylether and extracted with 1 M citric acid solution. The aqueous extracts were combined and basified with sodium bicarbonate solid to pH>7. The basic aqueous layer was extracted with ethyl acetate and the organic layer was washed with brine. The organics were dried over anhydrous sodium sulfate and concentrated under reduced pressure. Purification by column chromatography (50-100% ethyl acetate in hexanes) gave the product (173 mg, 12%). 400 M Hz 1H-NMR (CDCl3) δ: 7.26 (d, J=8.7 Hz, 2H), 6.65 (d, J=8.7 Hz, 2H), 3.66 (brs, 1H), 3.31 (s, 1H), 1.67 (s, 3H), 1.64 (s, 3H), 1.20 (s, 9H). was added dropwise at −78° C to warm to room temperature After being stirred for 18 h at room temperature the reaction mixture was poured into ice cooled saturated sodium bicarbonate solution The aqueous layer was extracted with ethyl acetate The combined organic layer was washed with saturated sodium bicarbonate solution and brine dried over anhydrous sodium sulfate The dried solution was filtered the filtrate was concentrated to dryness The residue was diluted with diisopropylether extracted with 1 M citric acid solution The basic aqueous layer was extracted with ethyl acetate the organic layer was washed with brine The organics were dried over anhydrous sodium sulfate concentrated under reduced pressure Purification by column chromatography (50-100% ethyl acetate in hexanes)

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

Procedure: To a solution of 2-Methyl-2-propanesulfinamide (1.47 g) and acetone (0.98 ml) in THF (24 ml) chilled to 0° C. was added Ti(OEt)4 (5.36 ml) dropwise over the course of 15 minutes. After being stirred at room temperature for 3 days, the reaction mixture was quenched by the rapid addition into ice cooled saturated sodium bicarbonate solution. The suspension was filtered through glass fiber filter paper, washing with ethyl acetate. The filtrate was washed with saturated sodium bicarbonate solution and brine. The organics were dried over anhydrous sodium sulfate and concentrated under reduced pressure. Purification by column chromatography (10-60% ethyl acetate in hexanes) gave the product (0.923 g, 47%). 400 M Hz 1H-NMR (CDCl3) δ: 2.34 (s, 3H), 2.18 (s, 3H), 1.23 (s, 9H). the reaction mixture was quenched by the rapid addition into ice cooled saturated sodium bicarbonate solution The suspension was filtered through glass fiber filter paper washing with ethyl acetate The filtrate was washed with saturated sodium bicarbonate solution and brine The organics were dried over anhydrous sodium sulfate concentrated under reduced pressure Purification by column chromatography (10-60% ethyl acetate in hexanes)