基于手性亚砜的膦手性膦配体设计及应用

Asymmetric catalysis is one of effective methods to access chiral compounds,in this field,the key issue is the design of chiral ligand,which play an important role on catalytic activities and stereoselectivities. P-chirality is an important chiral source and p-stereogenic ligand is always one of attractive topic in organic chemistry. In this project, we will attemp to develop a concise approach to synthesis a new class of sulfoxide-P-stereogenic ligands.Study these ligands in trans-metal(palladium,iridium and rhodium) catalyzed asymmetric carbon-carbon bond forming reactions,perticullarly in the reactions of construction of chiral quaternary centers, stereoselective and regioselective conjugated additions and so on.Furthermore, in this project, we will also systematically study the relationships among the structure of ligands(electronic and stereohindrance),different metals, different substrates and other reaction factors.This project will provide a fundamental support for the development of novel chiral catalytic technology.

不对称催化获取手性化合物最有效的手段之一，其中，手性配体的设计是核心，配体结构对催化活性和立体控制起着关键作用。膦手性是一种非常重要的手性源，膦手性配体一直是有机化学领域的热点之一。本项目拟利用叔丁基亚砜优异的立体诱导能力，发展简洁的合成新型亚砜膦手性（膦潜手性）配体的方法，研究这类配体的钯、铱和铑等过渡金属催化的不对称碳-碳键生成反应，特别是在构建手性季碳中心、立体及区域选择性共轭加成等反应中，配体结构的电性、位阻与不同金属物种、不同底物及其它反应参数等之间的规律性，为发展新的手性催化技术提供理论基础。

本项目1）设计了一类双功能的膦潜手性的双手性亚砜配体，配体的两个亚砜在催化反应中起不同的作用：与金属配位和作为氢键的受体。这类配体在钯催化不对称烯丙基取代反应中，成功地实现对挑战性1，3-非对称底物与吲哚的动态动力学转化；2）设计了一个新的C2对称性的手性双亚砜膦配体，实现了其铑络合物催化芳基硼酸对挑战性底物：γ-芳基- β,γ-不饱和酮酰胺/酸酯的1，4-共轭加成，反应获得了高区域选择性、高活性和高对映选择性；3）利用手性亚砜膦配体，成功地实现不对称铜催化碳硼键的构建：手性α-胺基硼酸和手性偕二芳基烷基硼化合物。