In the presence of chiral thiourethane ligands [Cu (MeCN) 4] BF4 forms active catalysts for the conjugate addition of MeMgBr, ZnEt2 and AlR3 (R= Me, Et) to non-3-en-2-one, hept-3-en- 2-one, and 5-methylhex-3-en-2-one. Enantioselectivities of up to 51% are realised for these difficult substrates; for cyclohex-2-enone an ee of 42% is attained.