Polymerization of optically active 2-fluorophenyl-4-fluorophenyl-2-pyridylmethyl methacrylate with anionic and radical initiators: Stereospecificity and helix-sense selection

Stereospecific Living Radical Polymerization: Dual Control of Chain Length and Tacticity for Precision Polymer Synthesis

“…However, the polymers showed large optical rotations opposite in sign to the rotation of the starting monomer, in which the prevailing in one-handed helix was amplified due to the steric effect of the chiral side group . A similar tendency was observed for the polymerization of another chiral and bulky methacrylate with fluorinated substituents (CM- 13 ) . Furthermore, the introduction of a chiral auxiliary into the ethylene-linkage of PDBSMA (CM- 14 ) resulted in the self-induction of the prevailing one-handed helicity without loss of the highly isotactic specificity …”

“…301 A similar tendency was observed for the polymerization of another chiral and bulky methacrylate with fluorinated substituents (CM-13). 302 Furthermore, the introduction of a chiral auxiliary into the ethylene-linkage of PDBSMA (CM-14) resulted in the self-induction of the prevailing one-handed helicity without loss of the highly isotactic specificity. 303 Since the report by Wulff et al that the asymmetric cyclopolymerization of distyryl monomers with a chiral linkage (CM-15) resulted in main-chain chiral polymers, various divinyl monomers with a chiral template were intensivelystudiedmainlyinordertoobtainchiralpolymers.…”

Synthetic Helical Polymers: Conformation and Function

“…The stereochemistry of 2F4F2PyMA ( 28 ) polymerization was also investigated. , The optically pure (+)-2F4F2PyMA ([α] 365 +28°) afforded polymers with a relatively low mm content and a low optical activity either by the anionic polymerization with DPEDA−Li in THF at −78 °C (mm/mr/rr = 70/30/∼0, [α] 365 −82°) or by the radical polymerization in toluene using ( i -PrOCOO) 2 at 40 °C (mm/mr/rr = 54/27/19, [α] 365 −2°) . The monomer design of 2F4F2PyMA was not as effective as that of PPyoTMA in controlling the polymerization stereochemistry.…”

“…The stereochemistry of 2F4F2PyMA (28) polymerization was also investigated. 88,89 The optically pure ). 89 The monomer design of 2F4F2PyMA was not as effective as that of PPyoTMA in controlling the polymerization stereochemistry.…”

“…88,89 The optically pure ). 89 The monomer design of 2F4F2PyMA was not as effective as that of PPyoTMA in controlling the polymerization stereochemistry.…”