Synthesis of (1R,4S)-(-)-4-tert-Butyldimethylsiloxy-2-Cyclopentenyl Acetate from (1R,4S)-(+)-4-Hydroxy-2-Cyclopentenyl Acetate -- DMAP as Catalyst

L.A. Paquette and T.M. Heidelbaugh, Org. Synth., 73, 44, (1996)

1. To (1R,4S)-(+)-4-hydroxy-2-cyclopentenyl acetate (7.67 g, 54 mmol), DMAP (660 mg, 5.4 mmol), triethylamine (17 mL, 122 mmol), and dichloromethane (175 mL), cooled to 0° C with an ice-water bath under a nitrogen a®osphere, tert-butyldimethylsilyl chloride (10.24 g, 68 mmol) is added in one portion.
2. The ice-water bath is removed and the mixture is allowed to warm to room temperature and is stirred for 3 h.  At this point, more silyl chloride is added if necessary and stirred for another 2 h.  (The progress of the reaction is easily monitored by TLC analysis.  Silyl chloride is added until the starting hydroxy-acetate is no longer detected.)
3. After 5 h, water (200 mL) is added, the mixture transferred to a separating funnel, and the organic phase separated.  The aqueous phase is extracted with dichloromethane (3 x 100 mL) and the combined organic layers are washed with saturated sodium bicarbonate solution (100 mL) and brine (100 mL) prior to dyring over anhydrous magnesium sulfate.  After filtration and solvent removal, the resulting yellow oil is purified by bulb-to-bulb distillation at 0.4 -0.6 mm (pot temperature 80-100°C) to give (1R,4S)-(-)-4-tert-butyldimethylsiloxy-2-cyclopentenyl acetate (10.67-11.08 g, 77-80% yield) as a colorless liquid.