反应详情

温度

85 °C

To a mixture of tert-butyl 4-bromobenzoate (10.07 g, 39.2 mmol), K3PO4 (20.19 g, 95 mmol), and dimethyl malonate (4.50 mL, 39.2 mmol) was added toluene (69 mL), Pd2(dba)3 (975 mg, 1.08 mmol), and P(tert-Bu)3 (12.8 mL, 10% wt. in hexanes, 4.3 mmol). The reaction mixture was degassed and heated to 85° C. After 2 d, the reaction mixture was diluted with ethyl acetate, washed with water (1×), brine (1×), dried over MgSO4, filtered, and concentrated. Purification by flash column chromatography on silica gel (5% to 20% ethyl acetate in hexanes) gave dimethyl [4-(tert-butoxycarbonyl)phenyl]malonate as a low melting white solid: 1H NMR (600 MHz, CDCl3) δ 7.98 (d, J=8.5 Hz, 2H), 7.45 (d, J=8.2 Hz, 2H), 4.70 (s, 1H), 3.76 (s, 6H), 1.58 (s, 91-1); ESIMS calcd 331.1 (M++Na), found 331.1 (M++Na). General Procedure for the Amidation of Dimethyl [4-(tert-butoxycarbonyl)phenyl]malonate

1. customThe reaction mixture was degassed
2. additionthe reaction mixture was diluted with ethyl acetate
3. washwashed with water (1×), brine (1×)
4. dry with materialdried over MgSO4
5. filtrationfiltered
6. concentrationconcentrated
7. customPurification by flash column chromatography on silica gel (5% to 20% ethyl acetate in hexanes)