Synthesis of polymers containing chiral 1,2-diamine derivatives and their application to asymmetric reactions

Abstract Polymer-supported chiral 1,2-diamine derivatives have been prepared. The polymers containing free 1,2-diamine moiety were applied to enantioselective hydrogenation catalyst by combination with RuCl2-BINAP complex. Asymmetric hydrogenation of aromatic ketones was performed by means of the polymeric catalyst derived from these polymers to give the chiral secondary alcohols with high ee in quantitative conversion. The polymers containing 1,2-diamine monosulfonamide were applied to enantioselective transfer hydrogenation catalyst by combination with RuCl2-p-cymene complex. Asymmetric transfer hydrogenation of aromatic ketones was performed by means of the polymeric catalyst to afford the chiral secondary alcohols. A high level of enantioselectivities up to 99 % ee was attained in neat water by using the polymeric catalyst prepared from quaternary ammonium salt-type polymer support.

摘要：制备了聚合物负载的手性1,2 - 二胺衍生物。将含有游离1,2 - 二胺部分的聚合物与RuCl₂ - BINAP配合物结合，应用于对映选择性氢化催化剂。利用由这些聚合物衍生的聚合物催化剂对芳香酮进行不对称氢化，以定量转化的方式得到了具有高对映体过量值（ee）的手性仲醇。将含有1,2 - 二胺单磺酰胺的聚合物与RuCl₂ - 对异丙基苯配合物结合，应用于对映选择性转移氢化催化剂。利用该聚合物催化剂对芳香酮进行不对称转移氢化以得到手性仲醇。通过使用由季铵盐型聚合物载体制备的聚合物催化剂，在纯水中实现了高达99% ee的高对映选择性。