Ni-Catalyzed chemoselective alcoholysis of N -acyloxazolidinones

Although N -acyloxazolidinone-based (catalytic) asymmetric synthetic methodologies occupy an important position in modern organic synthesis, the catalytic cleavage of a chiral auxiliary remains underdeveloped. We report the Ni(cod) 2 /bipyr.-catalyzed alcoholysis of N -acyloxazolidinones to deliver esters. The reaction is broad in scope for both N -acyloxazolidinone substrates and alcohol nucleophiles, and displays good functional group tolerance and excellent chemoselectivity. A gram-scale methanolysis allowed the enantioselective synthesis of the C22–C26 segment of a close analogue of the potent immunosuppressant agent FK506.