小分子的识别与选择性反应

分子间通过非共价相互作用而形成的定向识别在许多生物和化学过程中起重要的控制作用。本项目拟通过计算机模拟、合成以及多维多核核磁共振技术研究青蒿素类似物与靶分子；番荔枝内酯类似物与金属离子；有机钒与蛋白酪氨酸酶的分子模拟物等体系的相互作用即分子识别；根据分子识别现象，设计手性催化剂发展对映选择性氧化、还原和碳碳键形成反应。

In this project, the research has been undertaken around the recognition of.small molecules and selective reactions. The interaction of Qinhaosu with several types of.small molecules and the biochemical mechanism of Qinghaosu has been studied. These.studies have led to propose new hypothesis on the mechanism of Qinghaosu. A new class of.structurally simpler analog has been designed and synthesized, which showed interesting.bioactivities. These studies will found the basis for future studies on biochemical mechanism.and structure-activity relationship. A highly regio and diastereo-selective Grignard reagent.addition to malimide have been observed. In situ, multi-nuclear-NMR studies and.computational calculations allowed revealing that the non-bonding interactions and orbital.coefficients are origins of the observed high position-recognition (selectivity) and.face-recognition (Diastereoselectivity). A systematic study on chiral catalysts has led to the.development of both, a catalytic asymmetric hetero-Diels-Alder reaction in high yield.(52-92%) and high ee (88-99%); and a catalytic asymmetric sulfoxidation method in good ee.(56% ee for S and 96% ee for R-enantiomer). A new chiral carbanionic pyrrolidine.synthon, a new chiral carbanionic 2-pyrrolidinone synthon and a new chiral piperidine.synthon have been developed. Based on these new synthons, several selective reactions and.synthetic methods have been developed, which also led to the total synthesis of several.chiral drugs and natural products