Asymmetric Direct Remote Michael Addition Reactions of Allyl Furfurals via Dearomative Trienamine and Tetraenamine Catalysis

2‐Allyl‐3‐furfural could generate dearomative trienamine species in the presence of a chiral secondary amine, and underwent an asymmetric remote ϵ‐regioselective Michael addition reaction with isatin‐derived α,α‐dicyanoalkenes. Meanwhile, the more challenging dearomative tetraenamine intermediate from 5‐allyl‐2‐furfural could be similarly utilized in very remote η‐regioselective Michael additions. In general, good yields with moderate to high enantioselectivity were obtained by employing a concerted activation strategy of bifunctional secondary amine/thiourea catalysts. Mike is being direct: The dearomative trienamine or tetraenamine species generated from 2‐allyl‐3‐furfural or 5‐allyl‐2‐furfural and chiral secondary amines could react with isatin‐derived α,α‐dicyanoalkenes, affording the very remote ϵ‐ or η‐regioselective Michael addition adducts, respectively, in good yields with moderate to high enantioselectivity.