Simple sulfonamide organocatalysts deliver unparalleled efficiency in the asymmetric Michael–hemiacetalization cascade.

Addition of prochiral cyclic 1,3‐diketones to Michael acceptors applying bifunctional Cinchona‐derived squaramides resulted in chiral adducts with stereoselectivities of up to 99% ee and allowed for desymmetrization of the nucleophile. These labile hemiacetal intermediates were transformed to new 1,4‐dihydropyridines with high diastereoselectivities and no erosion of optical purity. Their further oxidation to pyridine followed by Fisher indolization provided chiral pyridine‐indoles.

Indolines could be successfully applied in the diversity of CH bond functionalization of benzenoid moiety without the competition between sp 3 H and sp 2 H activations thereby offering an access to functionalized heterocycles including the indoles. The metal‐catalyzed transformations proceeding the CH functionalizations of C4, C5, C6, and C7 position will be covered in the article along with applications to analogs systems in tetrahydroquinolines and tetrahydroisoquinolines.