不对称自诱导反应是指在反应过程中产物可以与催化剂结合控制反应的对映选择性，产物本身就是反应的手性来源。它的建立有望从根源上解决不对称催化的所有现实问题。然而不对称自诱导反应过程中产物与催化剂相结合，针对反应过程的机理研究也将更为复杂和富有挑战。实验发现，在钯配合物催化的Morita-Baylis-Hillman醋酸酯[3+3]环化反应中，产物参与了反应过程的手性控制，起到了不对称自诱导的作用，并首次证实不对称自诱导与温度以及M/L比例相关联。本项目拟以理论计算化学为主要手段，对该不对称自诱导的[3+3]环化反应的机理进行系统研究；理解反应温度、催化剂等因素对反应的影响；揭示反应过程中的不对称自诱导机制，探究手性放大作用；从理论上指导新型高效不对称自诱导反应的设计并进行实验验证。本项目的实施不仅可以推动不对称催化化学的理论发展，对探索生命手性起源也具有重要的科学意义。

The asymmetric autoinductive reactions, where products themselves could act as chiral source to control the enantioselectivity through combination with the catalysts, are hopeful to fundamentally solve all the intractable problems in the realm of asymmetric catalysis. The documented fact of products binding with the catalysts during the reaction sequence made mechanistic studies highly complicated and challenging. Experimental studies found that in the palladium-catalyzed Morita-Baylis-Hillman acetate [3 + 3] cyclization reaction, the product participated in the chiral control and played an autoinductive role in the reaction. Furthermore, the asymmetric autoinduction was, for the first time, verified to be associated with the temperature and the ratio of palladium to phosphine ligands. In this project, maneuver of theoretical calculations would be delivered to systematically study the mechanism of this reaction by explaining and understanding the effects of reaction temperature, catalyst, etc. on the reaction, with the aim of revealing the asymmetric autoinductive mechanism in the reaction process, discussing the asymmetric amplification effect, as well as directing the design of new types of highly-efficient asymmetric autoinductive reactions and arriving at the concomitant experimental verification. The successful implementation of this project is not only expected to promote the further development of theories in asymmetric catalysis, but is also of important scientific significance in exploring the origin of biological homochirality.