双功能MIO仿生催化剂的设计、合成及用于不对称反应的研究

不对称仿生催化具有反应条件温和，化学选择性好和立体专一性强等优点，顺应了绿色及可持续性发展战略的需要，是催化学科的一种重要发展趋势。不对称仿生催化的基石是仿生催化剂，因此，发展新型的仿生催化剂并用于不对称反应是一个具有重要意义的课题。本项目首次模拟生物体内氨基裂解酶的反应历程，在功能结构MIO中引入手性环境，再辅以氢键导向，设计并合成双功能MIO仿生催化剂，并将其应用于α,β-不饱和化合物的不对称胺化反应，MBH加成物的不对称烯丙基胺基化反应和环状化合物的不对称胺化开环反应。探讨双功能MIO仿生催化剂结构对反应的影响，反应底物与反应活性及选择性的规律、提出反应的过渡态及催化循环机理。通过此项目的完成，必将进一步推动不对称仿生催化的发展，为设计新型仿生催化剂提供新的思路与方法。

Asymmetric biomimetic catalysis has some advantages such as mild reaction conditions, good chemical selectivity and excellent stereospecificity, which complies with the demand of green and sustainable development strategy, and it is an important trend of asymmetric catalysis. The biomimetic catalyst is the cornerstone of asymmetric biomimetic catalysis. Therefore, it is of great significance to develop new biomimetic catalysts for asymmetric reactions. We first plan to simulate the reaction process of the functional structure of 4-methylideneimidazole-5-one (MIO) of ammonia-lyases in vivo to design and synthesize bifunctional MIO biomimetic catalysts with chiral skeleton and hydrogen bond group. Meanwhile, we will use the developed bifunctional MIO biomimetic catalysts in asymmetric amination of unsaturated substrates, asymmetric allyl amination of MBH adducts and asymmetric aminative ring-opening reaction of cyclic compounds. We will systemically study the relationship between the structure of bifunctional MIO biomimetic catalysts and activity or stereoselectivity, and disclose the possible transition state and the catalytic cycle mechanism. The realization of this project would provide useful information for the development of more effective catalysts.