A new enantioselective rhodium-catalyzed domino reaction is described that gives access to fused heterocycles by desymmetrization of alkyne-tethered cyclohexadienones. Two new C鈥揅 bonds and two stereocenters are formed in one step with good enantioselectivity. In contrast to prior reports, it was found that a vinylidene is not involved in the product formation but that syn-addition of the rhodium-aryl species onto the alkyne takes place.
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