瞬态配体导向催化的脂肪醛远程C(sp3)-H键的不对称芳基化反应

脂肪醛作为有机合成的重要结构单元，广泛存在于各类天然产物和药物中。目前为止，脂肪醛远程C-H键的直接不对称官能化反应还是有机合成的一个难题。我们通过设计系列手性瞬态配体，发展一类新颖的不对称催化模式：即在手性瞬态配体导向协助下进行钯催化脂肪醛远程C(sp3)-H键的不对称芳化反应。该类手性催化反应不同于目前已报道的不对称催化模式，主要以手性去对称芳基化和对映选择性芳基化的方式构建手性脂肪醛衍生物。预计该类催化模式能够快速、有效地实现脂肪醛化合物β位以及γ位的C(sp3)-H键的不对称官能化。此外，本项目还将探究手性瞬态配体结构以及构型对反应光学活性和收率的影响。

Aliphatic aldehydes as an important structural unit of organic synthesis, widely present in various kinds of natural products and drugs. So far, the direct asymmetric functionalization of the aliphatic aldehyde remote C-H bond is still a difficult problem in organic synthesis. This project will develop a novel asymmetric catalytic system employing series of well-designed chiral transient ligands, which means to achieve the palladium-catalyzed asymmetric arylation of remote sp3 C-H bonds of aiphatic aldehydes enabled by a transient ligand. This catalytic model will be used to construct chiral aliphatic aldehydes derivatives through chiral asymmetric and enantioselective arylation reactions, which is different from reported asymmetric catalytic models. It is expected that this kind of catalytic model can perform the asymmetric functionalization of β- and γ-sp3 C-H bonds of of aiphatic aldehydes in a fast and effective manner. In addition, this project will also explore the effects of chiral transient ligand structures and configurations on the optical activity and yield of reaction.