Highly regio- and stereoselective remote aziridination of 2,4-dienals has been developed, based on a vinylogous iminium-ion-dienamine catalytic cascade reaction. Transformations of the aziridine products into enantioenriched motifs are also demonstrated. Furthermore, the reaction concept is extended to include enantioselective 1,6-addition of thiols.

A general organocatalytic cross‐dienamine activation strategy to produce chiral multifunctionalized norcamphor compounds having a large diversity in substitution pattern is presented. The strategy is based on a Diels–Alder reaction of an amino‐activated cyclopentenone reacting with most common classes of electron‐deficient olefins, such as nitro‐, ester‐, amide‐, and cyano‐substituted olefins, chalcones, conjugated malononitriles, CF3‐substituted enones, and fumarates. The corresponding norcamphor derivatives are formed in good yield, excellent enantioselectivities, and with complete diastereoselectivity. Furthermore, it is demonstrated that quaternary stereocenters and spiro norcamphor compounds can be formed with high stereoselectivity. The present development provides a simple, direct, and efficient approach for the preparation of important norcamphor scaffolds.

A general organocatalytic cross-dienamine activation strategy to produce chiral multifunctionalized norcamphor compounds having a large diversity in substitution pattern is presented. The strategy is based on a Diels-Alder reaction of an amino-activated cyclopentenone reacting with most common classes of electron-deficient olefins, such as nitro-, ester-, amide-, and cyano-substituted olefins, chalcones, conjugated malononitriles, CF3-substituted enones, and fumarates. The corresponding norcamphor derivatives are formed in good yield, excellent enantioselectivities, and with complete diastereoselectivity. Furthermore, it is demonstrated that quaternary stereocenters and spiro norcamphor compounds can be formed with high stereoselectivity. The present development provides a simple, direct, and efficient approach for the preparation of important norcamphor scaffolds.

Oxadendralenes are integrated in a novel manner into a one-pot cascade utilizing synergistic catalysis for the construction of valuable and complex bicyclic heterocyclic scaffolds.

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