Helix-Sense-Selective Encapsulation of Helical Poly(lactic acid)s within a Helical Cavity of Syndiotactic Poly(methyl methacrylate) with Helicity Memory

We report a highly enantio- and helix-sense-selective encapsulation of helical poly(lactic acid)s (PLAs) through a unique "helix-in-helix" superstructure formation within the helical cavity of syndiotactic poly(methyl methacrylate) (st-PMMA) with a one-handed helicity memory, which enables the separation of the enantiomeric helices of the left (M)- and right (P)-handed-PLAs. The M- and P-helical PLAs with different molar masses and a narrow molar mass distribution were prepared by the ring-opening living polymerization of the optically pure l- and d-lactides, respectively, followed by end-capping of the terminal residues of the PLAs with a 4-halobenzoate and then a C₆₀ unit, giving the C₆₀-free and C₆₀-bound M- and P-PLAs. The C₆₀-free and C₆₀-bound M- and P-PLAs formed crystalline inclusion complexes with achiral st-PMMA accompanied by a preferred-handed helix induction in the st-PMMA backbone, thereby producing helix-in-helix superstructures with the same-handedness to each other. The induced helical st-PMMAs were retained after replacement with the achiral C₆₀, indicating the memory of the induced helicity of the st-PMMAs. Both the C₆₀-free and C₆₀-bound helical PLAs were enantio- and helix-sense selectively encapsulated into the helical hollow space of the optically active M- and P-st-PMMAs with the helicity memory prepared using chiral amines. The M- and P-PLAs are preferentially encapsulated within the M- and P-st-PMMA helical cavity with the same-handedness to each other, respectively, independent of the terminal units. The C₆₀-bound PLAs were more efficiently and enantioselectively trapped in the st-PMMA compared to the C₆₀-free PLAs. The enantioselectivities were highly dependent on the molar mass of the C₆₀-bound and C₆₀-free PLAs and significantly increased as the molar mass of the PLAs increased.