The design of a NHC‐catalyzed methodology for the straightforward access to hitherto unknown axially chiral N‐aryl phthalimides has provided a breakthrough in the field of multichirality control. Anticipating a formal (4+2) oxidative annulation, the use of NHC‐derived chiral dienolate as ambident partner toward N‐aryl maleimides unexpectedly yields original bis‐succinimide‐type compounds featuring a multichiral architecture with up to four stereogenic centers and two remote chiral axes. The overall pseudo‐three components reaction between an enal and two equivalents of a N‐aryl maleimide proceeds with excellent enantioselectivity and complete diastereoselectivity. This study illustrates the high synthetic potential of chiral NHC‐activated dienolates for the rapid and highly diastereo‐ and enantioselective preparation of underexplored atropisomers in the pentatomic series, featuring multiple stereogenic elements including challenging Csp2−N chiral axes. The practicality of this reaction is highlighted by a broad substrate scope and a scaled‐up synthesis. Moreover, the easy base‐induced transformation of the chiral bis‐succinimide precursors allows to prepare the initially planned N‐aryl phthalimide atropisomers with excellent retention of enantiopurity.

Phenylboronic acid was shown to mediate the multicomponent free‐radical carbocyanation of olefins and the addition of alkyl iodides to vinylsulfones. The reaction of the boronic acid with di‐tert‐butyl hyponitrite generates an aryl radical, which can selectively abstract an iodine atom from an alkyl iodide to form the key carbon‐centered radical precursor. Arylboronic acids are thus considered efficient tin surrogates in this free‐radical process.

The progress in enantioselective organocatalysis have enabled efficient and highly stereoselective syntheses of cyclobutane derivatives, through (2 + 2) annulation reactions, overcoming the geometrical constraints inherent to these small cyclic molecules. More importantly, and taking advantage of their strain-releasing fragmentation, some cyclobutane derivatives, especially cyclobutanones and cyclobutenones, can now be regarded as versatile four-carbon atoms units amenable to the enantioselective construction of larger rings by (4 + n) annulation reactions to produce, five-, six-, seven-and eightmembered cyclic products. These recent developments concerning the enantioselective synthetic chemistry of cyclobutane derivatives under organocatalytic conditions are reviewed herein.