反应详情

温度

25 °C

To a degassed solution of 5-tert-butoxycarbonylamino-3-(3-fluoro-4-nitro-benzyl)-4-oxo-tetra-hydro-thiopyran-3-carboxylic acid allyl ester (3.56 g, 7.6 mmol) and morpholine (1.4 mL, 15.2 mmol) in THF (50 mL) was added under argon Pd(PPh3)4 (0.092 g, 0.076 mmol) and the reaction mixture was stirred at 25° C. for 3 h. The reaction mixture was poured onto cold saturated NaHCO3 solution and extracted with EtOAc. Combined extracts were washed with brine, dried over MgSO4 and evaporated. The residue was re-dissolved in THF (10 mL) and kept at 25° C. for 3 h after addition of a catalytic amount of DBU. The title compound was obtained after evaporation and crystallization from diisopropylether as single diastereoisomer: TLC (hexane-EtOAc 1:2) Rf=0.38; HPLC RtA=2.17 min; ESIMS [M+NH4]+=402; 1H NMR (400 MHz, CDCl3): δ 8.0 (dd, 1H), 7.14 (m, 2H), 5.68 (m, 1H), 4.54 (m, 1H), 3.41 (m, 1H), 3.28 (dd, 1H), 3.14 (m, 1H), 2.84 (ddd, 1H), 2.69 (dd, 1H), 2.65 (m, 2H), 1.42 (s, 9H).

1. extractionextracted with EtOAc
2. washCombined extracts were washed with brine
3. dry with materialdried over MgSO4
4. customevaporated
5. dissolutionThe residue was re-dissolved in THF (10 mL)
6. waitkept at 25° C. for 3 h
7. additionafter addition of a catalytic amount of DBU