羰基二咪唑 (CDI) 与胺反应生成脲
Sulfonythiourea(470 mg, 1 mmol) was dissolved in 1 N NaOH (3 mL) and hydrogen peroxide (0.6 mL, 30%) was added. After 1 h stirring at room temperature the mixture was acidified with 2 N HCl and the precipitate filtered off and dried to give thetile compound (420 mg, 92% yield) as colorless solid.
【Heinrich C. Englertetc J. Med. Chem. 2001, 44, 1085-1098】
The primary amide species (2 mmol) was added to an oven-dried Radleys carousel tube followed by toluene (2 mL) and the amine species (2 mmol). Hydroxylamine hydrochloride was then added and the carousel tube was sealed before the reaction mixture was heated at 105 oC. After being allowed to cool to room temperature, the solvent was removed in vacuo on a rotary evaporator and 20 mL dichloromethane added. The reaction mixture was then washed with water (2 x 30 mL) to remove the hydroxylamine hydrochloride, and the resulting organic layer was dried over MgSO4. The solution was concentrated in vacuo to give product.
【C. Liana Allen,* Benjamin N. Atkinson, Angewandte Chemie, International Edition, 2012, 51(6), 1383-1386】
Cu(OAc)2 (18 mg, 0.1 mmol), 1(135 mg, 1 mmol), aniline (121 mg, 1.3 mmol), and tert-amyl alcohol (2 mL) were added successively to a Schlenk tube (25 mL) equipped with a magnetic stirrerbar. The Schlenk tube was then closed and the resulting mixture was stirred at 140 oC for 14 h under an argon atmosphere. The accumulated ammonia gas in the pressure tube was then released under argon protection, and the reaction mixture was stirred at 140 oC for another 2 h. After cooling down to room temperature, the reaction solvent was removed under vacuum. The residue was directly purified by flash chromatography on silica gel eluting with heptane/ethanol (25:1) to give the desired compound as a white solid (165mg, 78% yield).
【Min Zhang，Angewandte Chemie,International Edition, 51(16), 3905-3909, 2012】