Synthesis of Optically Active Helical Polycarbenes through Helix-Sense-Selective Polymerization Strategy and Their Application in Chiral Separation

In this work, helical polycarbenes with optical activity were designed and facilely synthesized through the helix-sense-selective polymerization (HSSP) of the diazoacetate monomer with a dimethylbenzyl ester pendant catalyzed by pi-allylPdCl with chiral phosphine ligands at room temperature. The polymerization was carried out in a living and controlled style, and a range of helical polycarbenes with the desired number-average molecular weights and narrow molecular weight distributions were obtained. Circular dichroism and UV-vis analyses revealed that these polycarbenes exhibited a stable helical conformation with a preferred handedness, and their helical directions were dependent on the chirality of the chiral phosphine ligands. Further studies showed that the helical conformation of the obtained polycarbenes was from the polymeric backbone rather than the intermolecular aggregation in the solutions. Moreover, the prepared, optically active, helical polycarbenes possessed excellent enantioselective crystallization ability for threonine racemates. The enantiomeric excess (e.e.) of the induced crystals could be up to 83% via utilizing the prepared helical polycarbenes as a chiral separation agent.

Automated summary

Helical polycarbenes with optical activity were designed and synthesized in an environmentally friendly manner. These polymers exhibited stable helical conformations with preferred handedness and showed efficient chiral separation ability.