Synthesis of BINOL-thiourea Derivatives

Herein a convenient synthesis of BINOL-thiourea derivatives I, II and III via the reaction of phosphorylisothiocycanide C with amines was described in modest yield.The compound was used for next step without further purification (Yield: 88%). Synthesis of compound CTo a solution of 2 (0.12mol) in acetonitrile (20mL), KSCN (0.25mol) was added gradually with stirring, and the mixture was stirred at 65°C for 10 hours, which was filtrated and extracted with dichloromethane (15mL*2), the solvent was evaporated under reduced pressure to give a yellow liquid, which was used for the next step without further purification. The synthesis of I, II and IIIGeneral procedure: To a mixture of 3 (10mmol) in chloroform (30mL), a solution of aniline (10mmol) in chloroform (10mL) was added drop wise with stirring.The mixture was refluxed until reaction completion was detected by thin-layer chromatography.The solvent was evaporated under the reduced pressure, the residue was diluted with ether (10mL) and cooled in ice-water bath, the crude product was crystallized with DMF-H 2 O to give the target compound.Compound I: White solid, mp: 152-154 o C, yield: 64%.