A. N-tert-Butoxycarbonyl-2-bromopyrrole. A dry, 500-mL, three-necked, round-bottomed flask is equipped with a magnetic stirring bar, two solid addition funnels, and a three-way stopcock attached to a balloon filled with nitrogen. To the flask are added 4.5 g (67.2 mmol) of pyrrole (Note 1) and 180 mL of tetrahydrofuran (Note 2). The flask is evacuated and purged with nitrogen (Note 3). The stirred solution is cooled to −78°C with a dry ice-acetone bath (Note 4) and a catalytic amount (ca. 0.1 g) of azoisobutyronitrile (AIBN) (Note 5) is added via a solids addition funnel. After 5 min, 9.57 g (33.6 mmol) of 1,3-dibromo-5,5-dimethylhydantoin (Note 6) is added over a 20-min period via a solids addition funnel. The light-green mixture is stirred for an additional 10 min, then allowed to stand for 2 hr, keeping the temperature below −50°C. The solution is filtered by suction into a dry, 500-mL, round-bottomed flask that has been cooled to −78°C in a dry ice-acetone bath. The flask is equipped with a magnetic stirring bar and a three-way stopcock attached to a balloon filled with nitrogen. To the stirred dark-green solution is added 2.71 g (26.9 mmol) of triethylamine followed immediately by addition of 20.4 g (93.9 mmol) of di-tert-butyl dicarbonate and a catalytic amount (ca. 0.1 g) of 4-dimethylaminopyridine (Note 7). The flask is evacuated and purged with nitrogen (Note 3). The mixture is stirred for 8 hr while it is allowed to warm to room temperature (Note 8). The solvent is removed under reduced pressure at room temperature and 100 mL of hexane is added to the crude product, which is washed with deionized water (3 × 100 mL), dried over sodium sulfate, and concentrated under reduced pressure at room temperature. The crude product is purified by chromatography on amine-treated neutral silica (270 g) using hexane as the eluent (Note 9). The fractions containing the product are identified by TLC, combined, and concentrated under reduced pressure at room temperature to yield compound 1 as a colorless oil (13.5–14.7 g, 82–89%) (Note 10).

B. N-tert-Butoxycarbonyl-2-trimethylsilylpyrrole. A solution of N-tert-butoxycarbonyl-2-bromopyrrole (13.5 g, 54.9 mmol) in 40 mL of hexane is added to 200 mL of tetrahydrofuran (Note 2) in a dry, 500-mL, two-necked, round-bottomed flask equipped with a magnetic stirring bar, rubber septum, and a three-way stopcock attached to a balloon of nitrogen. The flask is evacuated and purged with nitrogen (Note 3). The stirred mixture is cooled to −78°C and 34.3 mL of 1.6 M butyllithium in hexane (Note 10) is added slowly via syringe over a 10-min period, during which time the colorless solution becomes brown. After an additional 10 min, 13.4 g (124 mmol) of chlorotrimethylsilane (Note 11) in 10 mL of tetrahydrofuran (Note 3) is added via syringe over a 10-min period. Stirring is continued and the mixture is allowed to warm to −30°C over a 1-hr period. The reaction mixture is quenched with saturated aqueous sodium bicarbonate (10 mL) at which point a dark red-purple color develops. After warming to 0°C, the solvent is removed under reduced pressure and the product is extracted into 300 mL of hexane. The organic layer is washed twice with 150 mL of water and then dried over anhydrous sodium sulfate. The solvent is removed under reduced pressure, and the residue is distilled twice using a Kugelrohr oven at 85°C and 0.15 mm to give the pure product 2 (10.5–11.1 g, 80–85%) (Note 12).