反应详情

To a solution of (R)-tert-butyl 3-phenylmorpholine-4-carboxylate 7 (41.55 g, 157.66 mmol) in CH2Cl2 (400 mL) was added [bis(trifluoroacetoxy)-iodo]benzene (74.25 g, 172.7 mmol, 1.1 eq.) followed by I2 (40 g, 157.6 mmol, 1 eq.) at room temperature (The reaction was exothermic on this scale, the temperature was maintained at room temperature by means of a water bath!). The reaction mixture was stirred at room temperature for 30 minutes. The reaction mixture was diluted with CH2Cl2 (˜200 mL) and washed with sat. aq. NaHCO3 (2×750 mL), sat. aq. Na2S2O3 (2×500 mL) and brine (1 L). The organic layer was dried over Na2SO4 filtered and concentrated in vacuo leading to a brown oil containing the desired product. The residue was purified by automated column chromatography (silica column (1.6 kg); gradient heptanes/EtOAc 0 to 15%). The separation was not optimal, the product-containing fractions were concentrated affording a white solid contaminated with some (˜10%) iodobenzene and starting material. Trituration in pentane (2 mL/g) afforded material of sufficient purity (22.7 g, 58.3 mmol) was isolated in 37% yield.

1. washwashed with sat. aq. NaHCO3 (2×750 mL), sat. aq. Na2S2O3 (2×500 mL) and brine (1 L)
2. dry with materialThe organic layer was dried over Na2SO4
3. filtrationfiltered
4. concentrationconcentrated in vacuo
5. additioncontaining the desired product
6. customThe residue was purified by automated column chromatography (silica column (1.6 kg); gradient heptanes/EtOAc 0 to 15%)
7. customThe separation
8. concentrationthe product-containing fractions were concentrated
9. customaffording a white solid
10. customwas isolated in 37% yield