Diastereodivergent synthesis of 4-oxocyclohexanecarbaldehydes by using the modularly designed organocatalysts upon switching on their iminium catalysis

The cinchona thiourea moiety in the self-assembled modularly designed organocatalysts (MDOs) switches off the iminium catalysis of these catalysts. In this study, it was found that the inhibited iminium catalysis could be switched on by using an appropriate weak acid and that, once the iminium catalysis was switched on, these catalysts could be applied for the highly stereoselective and diastereodivergent synthesis of 4-oxocyclohexanecarbaldehydes via a domino reaction between ketones and α,β-unsaturated aldehydes. The inhibited iminium catalysis of the MDOs was switched on by using trans -cinnamic acid and the activated MDOs were used for catalyzing the domino Mannich condensation/Michael/Michael reaction between ketones and α,β-unsaturated aldehydes.