Complementary Induction of Right- and Left-Handed Helical Structures by the Positioning of Chiral Groups on the Monomer Units: Introduction of (-)-Menthol as Side Chains of Poly(quinoxaline-2,3-diyl)s.

Abstract

Poly(quinoxaline-2,3-diyl) bearing menthyloxymethyl side chains derived from (-)-menthol at the 6- and 7-positions of the quinoxaline ring showed a single, right-handed helical structure in chloroform. Upon introduction of the same (-)-menthol-derived side chains into the 5- and 8-positions, a single, left-handed helical structure was formed in chloroform. The former poly(quinoxaline-2,3-diyl)s showed solvent-dependent inversion of the helical sense in 1,1,2-trichloroethane to form a left-handed helical structure with high screw sense purity. Copolymers bearing both menthyloxymethyl and o-(diphenylphosphino)phenyl groups in their side chains served as highly enantioselective chiral ligands in the palladium-catalyzed hydrosilylation of styrene.