Copper-catalyzed asymmetric 1,4-, 1,6-and 1,2-conjugate addition of Grignard reagents is an important method to build up a carbon chiral center, which exists in the key intermediates of many natural products and chiral drugs. In this paper, the copper-catalyzed asymmetric 1,4-, 1,6-and 1,2-conjugate addition of Grignard reagents to α,β-unsaturated compounds is summarized systematically, and such acceptors as α,β-unsaturated ketones, esters, lactones, aldehydes, thioesters as well as sulfones are involved. In addition, the mechanism of asymmetric 1,4-conjugate addition is also introduced.
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