Rationally designed multifunctional supramolecular iminium catalysis: direct vinylogous Michael addition of unmodified linear dienol substrates.

The development of a direct vinylogous Michael addition of linear nucleophilic substrates is a long-standing challenge because of the poor reactivity and the considerable difficulty in controlling regioselectivity. By employing a rationally designed multifunctional supramolecular iminium catalysis strategy, the first direct vinylogous Michael addition of unmodified linear substrates to α,β-unsaturated aldehydes, to afford chiral 1,7-dioxo compounds with good yields and excellent regio- as well as enantioselectivity, has been developed.