Palladium(0)-Catalyzed Reaction of 9-Alkyl-9-Borabicyclo[3.3.1]Nonane with 1-Bromo-1-Phenylthioethene: 4-(3-Cyclohexenyl)-2-Phenylthio-1-Butene [entry]

Tatsuo Ishiyama, Norio Miyaura, Akira Suzuki
2003 Organic Syntheses   unpublished
A. 1-Bromo-1-phenylthioethene. A 300 mL, two-necked, round-bottomed flask is fitted with a magnetic stirring bar, a pressure-equalizing dropping funnel, and a reflux condenser to which a nitrogen inlet tube and an oil bubbler are attached, is flushed with nitrogen. In the flask are placed 13.6 g (100 mmol) of phenyl vinyl sulfide (Note 1) and 80 mL of ether (Note 2), and then cooled to ca. -78。C with a dry ice-methanol bath. Bromine (16.0 g, 100 mmol) is added dropwise over 30 min to the
more » ... solution. After warming up to room temperature, 40 mL of absolute ethanol, followed by a solution of 8 g (143 mmol) of potassium hydroxide in 80 mL of absolute ethanol are added dropwise to the resulting slightly red solution over 30 min. The light brown solution containing white precipitate of potassium bromide is stirred at room temperature for 2 hr. The precipitate is filtered off and the solvent is removed thoroughly by rotary evaporation. The residue is treated with 200 mL of ether and 200 mL of water. Then, the organic layer is separated, washed with brine (50 mL), and dried over anhydrous magnesium sulfate. After the evaporation of solvent by rotary evaporation, the residual oil is distilled under reduced pressure to give 17.2 g (80 %) of 1-bromo-1-phenylthioethene (Note 3) as a colorless liquid, bp 49-50。 C (0.07 mm).
doi:10.1002/0471264180.os071.12 fatcat:qy745owzfvddnhquqb7ggh2xia