Dimethyl malonate → Dimethyl [4-(tert-butoxycarbonyl)phenyl]malonate

Participants

Reaction Conditions

Reaction Steps

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 x), 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, 9H); ESIMS calcd 331.1 (M++Na), found 331.1 (M++Na).

Provenance & Evidence