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A wide variety of bioactive molecules contain stereogenic quaternary carbons, and developing methods for the construction of these stereocentres continues to be an active area of research. Now, it has been shown that a nickel-catalysed enantioconvergent coupling of tertiary alkyl electrophiles with alkenylmetal nucleophiles—which probably proceeds via a radical pathway—can form and set quaternary stereocentres efficiently under mild conditions.