Enantioselective Direct Bisvinylogous 1,6-Additions of β-Allyl-2-cyclohexenone to α,α-Dicyanodienes Through Trienamine Catalysis.

An asymmetric direct ϵ-regioselective bisvinylogous 1,6-addition reaction of β-allyl-2-cyclohexenone to β-substituted α,α-dicyanodienes was developed through trienamine catalysis of a bifunctional primary amine–thiourea compound. Excellent enantioselectivity (up to 97 % ee) was obtained even through such a remote reaction mode. In addition, more complex cyclic frameworks could be efficiently constructed with high stereoselectivity.