Synthesis of enzyme mimic dual activation catalyst and its application for asymmetric synthesis

以L-丝氨酸为原料，设计合成了一种含氧膦的双恶唑啉配合物（PM-Box），该配合物在刘易斯酸和碱的双重活化下，催化醛和烯丙基硅烷的不对称烯丙基化反应，得到相应的高烯丙醇，产率为48-74%，ee值为39-86%.通过~ 1 P NMR谱证实了烯丙基硅烷的活化作用<31>，PM-Box-Cu（OTf）_2配合物在亚胺与三甲基硅烷的不对称反应中起了有效的催化作用。例如，亚苄基-N-苄叉亚胺与三甲基硅烷在3mol%的PM-Box-Cu（OTf）_2催化下反应，得到相应的高烯丙基胺，产率为91%，ee值为90%，酮亚胺在3mol%的催化剂存在下的Strecker反应，产物ee值高达96%。

The asymmetric allylation reactions of aldehydes catalyzed by a 10 mol% bisoxazoline complex bearing a phosphine oxide moiety(PM-Box), which was newly designed and synthesized from L-serine, afforded the corresponding homoallylic alcohols in 48-74% yields with 39-86% ee. The reaction proceeds with the dual activation of the aldehyde and allylsilane by the Lewis acid and base of the catalyst. The evidence for the activation of the allylsilane was clarified by the ^<31>P NMR spectra.The PM-Box-Cu(OTf)2 complex worked effectively in asymmetric reaction of imines with trimethylsilylsilane. For example, a reaction of benzylidene-N-benzhydrilimene with trimethylsilylsilane in the presence of 3mol% of PM-Box-Cu(OTf)2 gave a corresponding homoallyl amine in 91% yield with 90%ee. Furthermore, Strecker reactions of ketimines in the presence of 3mol% of the catalyst afford the product up to 96%ee.