Over the last several years there has been a huge increase in the development and applications of new efficient organocatalysts for enantioselective pericyclic reactions, which represent one of the most powerful types of organic transformations. Among these processes are cycloaddition reactions (e.g., [3+2]; formal [3+3]; [4+2]; vinylogous [4+2] and 1,3-dipolar cycloadditions), which belong to the most utilized reactions in organic synthesis of complex nitrogen-and oxygen-containing heterocyclic molecules. This review presents the breakthrough realized in this field using chiral BINOL-derived phosphoric acids and N-triflyl phosphoramide organocatalysts.

An unprecedented organocatalytic three-component domino Knoevenagel/vinylogous Michael reaction starting from simple enolizable aldehydes, malononitrile, and nitroolefins is reported. This facile two-step domino process provides a straightforward stereoselective route to multifunctional vinyl malononitrile products (up to 82 % yield, 85:15 d.r.) containing a nitroalkane moiety, and contributes to the development of sustainability and atom economy. The application of the obtained domino products for synthesis of highly functionalized o-terphenyls (of high interest for materials science and medicinal chemistry) through subsequent new three-step domino reaction involving cyclization-tautomerization-aromatization steps, has been demonstrated.

A new strategy for the synthesis of biologically active quinoxalines by using versatile α‐nitro epoxides as starting compounds has been developed. In addition, the in situ organocatalytic epoxidation of electron‐poor nitro olefins followed by condensation with 1,2‐phenylenediamines to provide quinoxalines in one pot has been demonstrated.

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Combination of a novel organocatalytic three‐component two‐step domino reaction with a subsequent new three‐step domino process, starting from easily accessible nitroolefins, malononitrile, and arylacetaldehydes, allows an unprecedented easy access to challenging highly functionalized o‐terphenyls, which are of high interest for materials science and medicinal chemistry. For more information, see the Full Paper by S. B. Tsogoeva and co‐workers on page 6551 ff.