The Synthesis Of Poly (Menthyl Propenol) Derivatives And Their Research In Asymmetry Catalytic Reactions Of Carbonyl

Chiral catalyst has always been the hot spot of people attention. Chiral catalystscould be divided into small molecules catalysts and polymer-supported catalystsaccording to their type. Due to most of the reported small molecules chiral catalystshas an expensive cost and not easy to be recycled. More attention was focused on thePolymer-supported catalyst which has the advantage of recycling.More recently, our group have reported the synthesis of poly menthyl vinylketone (poly-MVK) which was a one-handed helical polymer with high opticalrotation. Because of the active carbonyl of the polymer chain, the structure of thepoly-MVK could be modified, which could be carried out in some asymmetriccatalytic research.The main researching contents are as following:(1)The Poly(menthyl propenol)(poly-MPO) was obtained by the reduction ofthe poly-MVK, Which was obtained by radical polymerization of the menthyl vinylketone (MVK). By reacting with epichlorohydrin and different amine, seven graft ofchiral amino alcohol onto Poly(menthyl propenol)(poly-MPO)-APO were prepared.(2)Seven kinds of (poly-MPO)-APO were used as the chiral ligands inasymmetric Henry reaction. The study found that the (poly-MPO)-APO in asymmetricHenry reaction show moderate induction effect. Also, the (poly-MPO)-APO wasrecovered and reused, which could keep the moderate induction effect, it means the(poly-MPO)-APO could be recycled.(3)Seven kinds of (poly-MPO)-APO were used as the chiral ligands inasymmetric reduction and addition of ketones. The study found the (poly-MPO)-APOin asymmetric reduction of ketones show low asymmetric induction effect, but inasymmetric addition of ketones show high asymmetric induction effect. Also, the(poly-MPO)-APO was recovered and reused, which could keep the same inductioneffect, it means the (poly-MPO)-APO could be recycled.(4)To determine the configuration of the poly-MPO, the1-menthyl propanolwhich was the corresponding monomer unit of poly-MPO was synthesized. And its drvalue was68:32by GC-MS. By comparing with the known object1-menthyl ethanol,we identified the main configuration of the1-menthyl propanol was S. Therefore, wecan conclude that the main configuration of the poly-MPO be also S.