New thiophosphates containing functionalized cyclic ketone derivatives as ligands have been stereoselectively prepared from readily available starting materials. Full axial stereoselectivity of the NaBH4 reduction of the carbonyl group in thiophosphates providing the corresponding thiols or sulfides has been demonstrated. The sulfides have been transformed into new functionalized cyclic Baylis–Hillman type adducts of defined configuration. The prospects for the useful synthetic application of these adducts appear to be very promising.
