Diisopropylamine → Methyl 4-(2-t-butoxycarbonyl-vinyl)-benzoate

Participants

Reaction Steps

To a solution of anhydrous i-Pr2NH (1.76 ml, 12.49 mmol) in anhydrous THF (30 ml) stirred at 0° C. under nitrogen, was slowly added a solution of n-BuLi (5.36 ml, 13.40 mmol, 2.5 M in hexane). After 30 min, LDA was cooled to −78° C. and t-butyl acetate (1.64 ml, 12.18 mmol) was added dropewise. After 30 min, a solution of methyl 4-formylbenzoate (1.00 g, 6.09 mmol) in anhydrous THF (10 ml) was slowly added. After 2 h, a solution of 2-chloro-4,6-dimethoxy-1,3,5-triazine (1.604 g, 9.14 mmol) in anhydrous THF (10 ml) was added. Then, the temperature was allowed to warm up to room temperature overnight. A suspension appeared. The reaction mixture was poured into a saturated aqueous solution of NH4Cl, and diluted with AcOEt. After separation, the organic layer was successively washed with H2O and brine, dried over MgSO4, filtered and concentrated. The crude product was purified by flash chromatography on silica gel (AcOEt/hexane:10/90→15/85) to give the title product VI (785 mg, 3.00 mmol, 49% yield) as a white solid. 1H NMR (300 MHz, CDCl3) δ(ppm): AB system (δA=8.04, δB=7.57, J=8.4 Hz, 4H), 7.60 (d, J=15.4 Hz, 1H), 6.46 (d, J=15.8 Hz, 1H), 3.93 (s, 3H), 1.54 (s, 9H). 13C NMR (75 MHz, CDCl3) δ(ppm): 166.72, 166.01, 142.31, 139.18, 131.33, 130.26, 127.99, 122.87, 81.11, 52.46, 28.40.

Provenance & Evidence