Abstract

Regiodivergent vinylogous aza-Morita–Baylis–Hillman reactions of 3-vinylcyclopent-2-en-1-one 1 were developed in a catalyst-controlled manner. While treatment of 1 with N-tosylarylaldimines 2 in the presence of DABCO gave the α-adducts as the sole regioisomer, that in the presence of DMAP gave the unusual γ-adducts in 87–96% regioselectivity.

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