Tetraethyltin → 3-Methoxy-4-ethyl-benzonitrile

Participants

Reaction Conditions

Reaction Steps

To a solution of 3-methoxy-4-hydroxybenzonitrile (13-1, 2.0 g, 13.4 mmol) in DCM (67 mL) at −78° C. was added diisopropylethylamine (3.0 mL, 17.4 mmol) followed by triflic anhydride (2.7 mL, 16.0 mmol) and stirred at −78° C. for 1 h. The mixture was poured into a separatory funnel containing a few pieces of ice and then partitioned between ice water and ether. The organic phase was washed with 1N HCl and then 10% Na2CO3, dried over Na2SO4, filtered and concentrated to yield a pale yellow oil. To a solution of this oil (2.7 g, 9.60 mmol) in DMF (96.0 mL) was added tetraethyl tin (3.80 mL, 19.2 mmol), bis(tri-t-butylphosphine) palladium(0) (0.491 g, 0.960 mmol) and LiCl (1.22g, 28.8 mmol) and the system was heated to 80° C. for 1 h in an oil bath. The mixture was partitioned between saturated NaHCO3 and EtOAc. The organic phase was washed with water, brine, dried over Na2SO4, filtered and concentrated. The crude material was purified by gradient elution on silica gel (0 to 20% EtOAc in hexanes) to afford the desired compound (13-2) as a pale yellow crystalline solid. ESI+MS [M+H]+ C10H11NO: 162.1 found, 162.2 required.

Provenance & Evidence