氮、磷、硅等杂原子手性中心的不对称氧化构筑

不对称催化氧化是手性合成的重要手段，现有研究局限于碳原子手性中心的不对称构筑，而对于杂原子手性中心的不对称氧化构筑研究仍基本属于空白，目前仅有硫醚的不对称氧化构筑亚砜硫手性中心的研究报道。氮、磷、硅等杂原子手性中心广泛存在于天然产物、合成药物和手性配体中，但是现有的催化不对称合成方法仍十分有限。为此，本项目拟设计、发展含有“埋藏式”氧化中心的手性廉价金属催化剂，分别通过对三级胺、三级磷和三级硅烷的不对称催化氧化，实现氮原子、磷原子和硅原子手性中心的不对称氧化构筑，为上述杂原子手性中心的不对称构筑提供新的思路和策略。拟开展的研究内容在不对称氧化和元素有机化学两大领域均具有重大的科学意义和创新性。

Catalytic enantioselective oxidation represents an important approach in the area of asymmetric synthesis. However, current studies predominantly focused on asymmetric oxidative construction of a carbon stereocenter, and catalytic enantioselective oxidative construction of a heteroatom stereocenter has remained scarcely explored. Existing studies have been restricted to asymmetric oxidation of sulfides affording chiral sulfones for constructing sulfur stereocenters. On the other hand, heteroatom stereocenters including nitrogen, phosphorus, and silicon moieties are widely occurred in numerous natural products, synthetic pharmaceuticals, and chiral ligands. However, limited asymmetric synthetic methods have been developed. Herein, in this proposal, the applicant will design and synthesize base-metal catalysts containing confined oxidative active site deeply buried within a highly sterically demanding chiral environment, and systematically explore the catalytic asymmetric oxidation of tertiary amines, tertiary phosphines, and tertiary silanes for asymmetric construction of respective nitrogen-, phosphorus-, and silicon-stereocenters. These studies will provide a new synthetic planning for heteroatom stereocenter containing compounds. We envision that this proposal has significant scientific sense and novelty in two research fields of “asymmetric oxidation” and “element organic chemistry”.