Chromium-catalyzed cross-coupling of methyl ketones with cyclic ketones to β-branched β,γ-unsaturated ketones are reported. Interestingly, single-crossed aldol condensation products are formed, even in reactions in which a mixture of products is possible. The reaction is highly chemoselective and regioselective. This catalytic route gives a unique opportunity to integrate the chemistry of the synthetic challenge cross-coupling reaction of ketones and the alkene migration reaction into a reaction pot.

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