An organocatalytic cascade reaction of 2-nitrocyclohexanone and α,β-unsaturated aldehydes with unusual regioselectivity.

An organocatalytic cascade reaction of 2-nitrocyclohexanone and alpha,beta-unsaturated aldehydes was developed. Bicyclo[3.3.1]nonanone products were obtained with good yields and excellent enantioselectivities. The reaction occurred with unusual regioselectivity. A dienolate-iminium activation mechanism was proposed. The products were transformed to eight-membered cyclic ketones with high enantioselectivity.