Synthesis of Optically Active Poly(diphenylacetylene)s Using Polymer Reactions and an Evaluation of Their Chiral Recognition Abilities as Chiral Stationary Phases for HPLC.
A series of optically active poly(diphenylacetylene) derivatives bearing a chiral substituent (poly-2S) or chiral and achiral substituents (poly-(2Sx-co-31-x)) on all of their pendant phenyl rings were synthesized by the reaction of poly(bis(4-carboxyphenyl)acetylene) with (S)-1-phenylethylamine ((S)-2) or benzylamine (3) in the presence of a condensing reagent. Their chiroptical properties and chiral recognition abilities as chiral stationary phases (CSPs) for high-performance liquid chromatography (HPLC) were investigated. Poly-2Sand poly-(2Sx-co-31-x) (0.06 < x < 0.71) formed a preferred-handed helical conformation with opposite helical senses after thermal annealing despite possessing the same chiral pendant (h-poly-2Sandh-poly-(2Sx-co-31-x)). Furthermore,h-poly-2Sandh-poly-(2S0.36-co-30.64) emitted circularly polarized luminescence with opposite signs.h-Poly-2Sshowed higher chiral recognition abilities toward a larger number of racemates than poly-2Swithout a preferred-handed helicity and the previously reported preferred-handed poly(diphenylacetylene) derivative bearing the same chiral substituent on half of its pendant phenyl rings.h-Poly-(2S0.36-co-30.64) also exhibited good chiral recognition abilities toward several racemates, though the elution order of some enantiomers was reversed compared withh-poly-2S.
Graduate School of Natural Science and Technology, Kanazawa University, Kakuma-machi, Kanazawa 920-1192, Japan. maeda@se.kanazawa-u.ac.jp.
Katsuhiro
K
Maeda
Graduate School of Natural Science and Technology, Kanazawa University, Kakuma-machi, Kanazawa 920-1192, Japan. amyrtt@gmail.com.
Miyuki
M
Maruta
Graduate School of Natural Science and Technology, Kanazawa University, Kakuma-machi, Kanazawa 920-1192, Japan. y.sakai.kanazawa.u@gmail.com.
Yuki
Y
Sakai
Graduate School of Natural Science and Technology, Kanazawa University, Kakuma-machi, Kanazawa 920-1192, Japan. ikai@se.kanazawa-u.ac.jp.
Tomoyuki
T
Ikai
Graduate School of Natural Science and Technology, Kanazawa University, Kakuma-machi, Kanazawa 920-1192, Japan. kanoh@se.kanazawa-u.ac.jp.
Shigeyoshi
S
Kanoh
D000480:Alkynes / Q000138:chemical synthesis* / Q000737:chemistry; D002851:Chromatography, High Pressure Liquid; D015394:Molecular Structure; D013329:Structure-Activity Relationship
D000480:Alkynes
chiral stationary phase; enantioseparation; helix; helix inversion; high-performance liquid chromatography (HPLC); poly(diphenylacetylene)