We report herein a strategy to construct enantiopure inherently chiral macrocycles, ABCD-type heteracalix[4]aromatics, through a catalytic enantioselective intramolecular C−N bond forming reaction. A chiral ligand-palladium complex was found to efficiently induce the inherent chirality of molecules during the macrocyclization process with ee values up to >99%. The resulting ABCD-type heteracalix[4]aromatics displayed excellent and pH-triggered switchable electronic circular dichroism and circularly polarized luminescence properties.

SuFEx reactions, in which an S−F moiety reacts with a silyl‐protected phenol, have been developed as powerful click reactions. In the current paper we open up the potential of SuFEx reactions as enantioselective reactions, analyze the role of Si and outline the mechanism of this reaction. As a result, fast, high‐yielding, “Si‐free” and enantiospecific SuFEx reactions of sulfonimidoyl fluorides have been developed, and their mechanism shown, by both experimental and theoretical methods, to yield chiral products.

The products of the SuFEx reaction between sulfonimidoyl fluorides and phenols, sulfonimidates, are shown to display dynamic covalent chemistry with other phenols. This reaction was shown to be enantiospecific, finished in minutes at room temperature in high yields, and useful for both asymmetric synthesis and sustainable polymer production. Its wide scope further extends the usefulness of SuFEx and related click chemistries.

Novel methods to make synthetic chiral polymers are highly desirable given their potential in a rapidly increasing number of bio‐inspired applications. The enantiospecific sulfur–fluorine exchange (SuFEx) reaction of chiral di‐sulfonimidoyl fluorides (di‐SFs) with diphenols, was used to produce high‐molecular‐weight chiral polymers with configurational backbone chirality. The resulting new class of polymers, polysulfonimidates, can be efficiently produced via this step‐growth mechanism for a wide range of di‐SFs and diphenols, yielding MnPS up to 283 kDa with a typical dispersity Đ around 1.6. The optical activity of the resulting chiral polymers is largely due to the intrinsic asymmetry of the S atoms (configurational chirality). Finally, the enantiospecificity (ee>98 %) of the polymerization reaction was demonstrated by the degradation of a disulfide‐containing polysulfonimidate. This novel route towards configurational main‐chain chirality opens up new approaches towards tailor‐made chiral polymers with precisely defined properties.