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

An asymmetric direct E-regioselective bisvinylogous 1,6-addition reaction of -allyl-2-cyclohexenone to -substituted ,-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.