Facile Synthesis Of Optically Active Helical Poly(phenyl Isocyanide)s Brushes On Silicon Surface And Their Chiral Resolution Ability And Synthesis Of Optically Active Helical Poly(phenyl Isocyanide)s

In this work,optically active helical poly(phenyl isocyanide)s were grafted onto silicon wafer via both the "grafting from" and "grafting to" strategies.First,triethoxysilanyl functionalized alkyne-Pd(II)initiator was anchored onto the surface of hydroxylated silicon wafer through silanization coupling reaction.The surface-initiated polymerization of phenyl isocyanide lead to the formation of poly(phenyl isocyanide)brushes grafted on silicon surface via the "grafting from" strategy.The polymerization was revealed to proceed in a living/controlled chain-growth manner,afforded the polymer brushes with controlled thickness.On the other hand,the polymer brushes can be prepared via "grafting to" strategy.Triethoxysilanyl terminated optically active helical poly(phenyl isocyanide)was firstly prepared under a controlled manner,which was grafted to the surface of a hydroxylated silicon wafer.The obtained polymer brushes possess a plenty of chiral microenvironment originated from the chirality of the helical poly(phenyl isocyanide)arms.Such chiral materials exhibited excellent chiral resolution ability.The enantiomeric excess(ee)value of the absorbed mode compound,methyl benzyl alcohol was up to 87%.In addition,a part of this paper focuses on the research of polymerization of phenyl isocyanide using achiral Pd(II)initiator with the presence of(R,S,r)/(S,Rs)-Wei-Phos as additive was found to proceed in helix-sense-selective manner.The polymerization of achiral phenyl isocyanide,4-isocyanobenzoyl-2-aminoisobutyric acid decyl ester by this method produced optically active helical polymer,whose chirality was solely come from the helical conformation without containing of any other chiral atoms.