Enzymatic synthesis and characterization of amphiphilic block copolymers of poly(ethylene oxide) and amylose

Amphiphilic A‐B block copolymers, ω‐methoxypoly(ethylene oxide)‐amylose copolymers (MPEO‐amylose), were synthesized by an enzymatic reaction using potato phosphorylase from an MPEO (M_w = 5.0×10³)‐maltopentaosylamine derivative as a primer and α‐D ‐glucose‐1‐phosphate as a substrate. MPEO‐amyloses with various molecular weights of amylose (DP = 26, 36, 73 and 112) were obtained. None of the MPEO‐amyloses (5 mg/ml) precipitate in water containing 10 vol.‐% DMSO even after 24 h. The MPEO‐amyloses effectively form complexes with iodine in water.     

Preparation of Polymer-Supported Chiral 1,2-Diamine as an Efficient Ligand for Asymmetric Hydrogenation Catalyst

An enantiopure 1,2-diamine having two phenolic hydroxy groups was synthesized, and attached to chloromethylated poly(styrene) through a benzyl ether linkage. The polymer-supported Ru precatalysts were prepared from the polymeric chiral 1,2-diamine and RuCl₂/BINAP complex. In the presence of t-BuOK the polymeric catalyst system worked well in asymmetric hydrogenation of aromatic ketones in a mixed solvent of 2-propanol and DMF. The insoluble polymeric catalyst was readily separated from the reaction mixture and reused at least several times without loss of the catalytic activity.