Configurationally Chiral SuFEx‐Based Polymers

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 M (n) (PS) 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.