Synthesis of Large Macrocycles with Chiral Sulfur Centers via Enantiospecific SuFEx and SuPhenEx Click Reactions

Here we report the first asymmetric synthesis of large chiral macrocycles with chiral sulfur atoms. Building on stereospecific SuFEx and SuPhenEx click chemistries, this approach utilizes disulfonimidoyl fluorides and disulfonimidoyl p-nitrophenolates which are efficient building blocks with two chiral sulfur centers, and diphenols to efficiently form novel S-O bonds. Characteristic results include the enantiospecific one-step synthesis of rings consisting of 21-58 members and characterization of both enantiomers ( R,R and S,S ) by e.g. X-ray crystallography.

Automated summary

In this study, the first asymmetric synthesis of large chiral macrocycles with chiral sulfur atoms is reported. The method utilizes efficient building blocks with two chiral sulfur centers and diphenols to form novel S-O bonds through stereospecific SuFEx and SuPhenEx click chemistries. The characteristic results include the enantiospecific one-step synthesis of rings consisting of 21-58 members and the characterization of both enantiomers (R,R and S,S) using X-ray crystallography.