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An NHC-catalyzed, diastereo- and enantioselective dimerization of enals has been developed. The use of Ti(Oi-Pr)(4) is a key element for the reactivity and selectivity of this process. The cyclopentenes are obtained with high levels of diastereo- and enantioselectivity and their synthetic utility is demonstrated by functionalization of the product alkene.

NHC-Catalyzed/Titanium(IV)−Mediated Highly Diastereo- and Enantioselective Dimerization of Enals