A novel unsymmetrical (S,S,S)-salen ligand bearing a derived chiral-BINOL was synthesized by the reaction of the condensation product of (1S,2S)-1,2-diaminocyclohexane mono(hydrogen chloride) with 3-adamanyl-5-tert-bu...A novel unsymmetrical (S,S,S)-salen ligand bearing a derived chiral-BINOL was synthesized by the reaction of the condensation product of (1S,2S)-1,2-diaminocyclohexane mono(hydrogen chloride) with 3-adamanyl-5-tert-butyl-2-hydroxybenzalde-hyde and 3-formoyl-2-hydroxy-2'-alkyloxy-1,1'-binaphthyl,which originated from (S)-1,1'-bi-2-naphthol via a four-step reaction.The cobalt complexes of this ligand,in conjunction with a nucleophilic cocatalyst,exhibited excellent activity in catalyzing asymmetric,regio-and stereo-selective copolymerization of CO2 and racemic propylene oxide.The highest record of kinetic resolution coefficient (Krel) was obtained with the use of binary catalyst system consisting of (S,S,S)-salenCo(III) complex 1c and bulky bis(triphenylphosphine)-iminium chloride (PPNCl).The resulting poly(propylene carbonate)s have more than 99% carbonate linkages and more than 98% head-to-tail content.展开更多
基金supported by the National Natural Science Foundation of China (20634040)National Basic Research Program of China (973 Program) (2009CB825300)the Outstanding Young Scientist Foundation of the National Natural Science Foundation of China (20625414)
文摘A novel unsymmetrical (S,S,S)-salen ligand bearing a derived chiral-BINOL was synthesized by the reaction of the condensation product of (1S,2S)-1,2-diaminocyclohexane mono(hydrogen chloride) with 3-adamanyl-5-tert-butyl-2-hydroxybenzalde-hyde and 3-formoyl-2-hydroxy-2'-alkyloxy-1,1'-binaphthyl,which originated from (S)-1,1'-bi-2-naphthol via a four-step reaction.The cobalt complexes of this ligand,in conjunction with a nucleophilic cocatalyst,exhibited excellent activity in catalyzing asymmetric,regio-and stereo-selective copolymerization of CO2 and racemic propylene oxide.The highest record of kinetic resolution coefficient (Krel) was obtained with the use of binary catalyst system consisting of (S,S,S)-salenCo(III) complex 1c and bulky bis(triphenylphosphine)-iminium chloride (PPNCl).The resulting poly(propylene carbonate)s have more than 99% carbonate linkages and more than 98% head-to-tail content.
