天然单萜烯不对称催化转化研究

Chiral fine chemicals are synthesized using the rich natural forest resources by asymmetric catalytic conversion methods, which is a new and important field. The asymmetric hydrogenation and epoxidation reactions of natural monoterpenes such as α-pinene, β-pinene et al, will be deeply investigated in this subject. Designing novel chiral heterogeneous catalytic system-catalytic properties-catalytic mechanism as the main line of the study, asymmetric hydrogenation/epoxidation mechanism of olefin as a guide, the following research will be carried out: The chiral polyaniline/derivatives will be prepared using the static homogeneous nucleation method, and the effects of chiral doping on asymmetric structures of polyaniline will be studied. Based on the theories of chiral induction, the nickel, cobalt-boron amorphous catalyst and chiral salen catalyst loaded by chiral polyaniline/derivatives will be designed; The inherent relationships between structures of polyaniline(oxidation/reduction unit ratio,substituent,coordination mode and chiral characteristics) and the catalystic activity, enantioselectivity and stability will be clarified. Through revealing the evolution law of the monoterpenes stereoregular (cis-trans isomerization and optical isomerization) induced in the chiral polyaniline/derivatives, the asymmetric catalytic conversion method and theory of monoterpenes will be established. The research results will promote development of chiral catalytic materials and relative catalytic mechanism, and provide new ideas for efficient conversion and effective usage of monoterpenes, which has important research value.

围绕我国丰富天然单萜烯资源不对称催化合成手性精细化学品这一新领域，对松节油主要成分α-蒎烯、β-蒎烯等单萜烯的不对称氢化/环氧化展开深入研究。以新型手性非均相催化体系构建-催化性能-催化机制为研究主线，以烯烃不对称氢化/环氧化机理为指导，开展如下研究：采用静态均相成核的方法制备手性聚苯胺/衍生物，探索手性掺杂对聚苯胺不对称结构的调变规律；基于手性诱导理论，采用化学还原、配位的方法构建手性聚苯胺负载镍、钴-硼系列非晶态催化剂及Salen系列新型非均相催化剂；深入研究并科学阐明聚苯胺的结构（氧化/还原单元比、取代基、配位方式）及手性特征与催化活性、化学、立体选择性的内在关系；通过揭示在手性聚苯胺/衍生物诱导下单萜烯立构（顺反异构与旋光异构）演变规律，建立单萜烯不对称催化转化的方法和理论。结果为我国单萜烯的高效转化、有效利用提供新思路，并将推动负载型手性催化材料的发展，具有重要的研究价值。

控制SO2的排放并有效利用已成为各个国家的战略性研究课题。烯烃/环氧化物与SO2催化共聚制备聚砜或聚亚硫酸脂是利用SO2的有效途径之一。但现有烯烃/环氧化物与SO2共聚采用自由基聚合机理，其共聚条件苛刻、共聚物分子量低、结构难以控制。本项目采用配位聚合机理，以手性纳米聚苯胺/衍生物固载Salen及过渡金属盐系列聚苯胺配合物为催化剂（聚苯胺既是配体又是载体），实现了高效、稳定地催化SO2与蒎烯等天然单萜烯不对称交替共聚，探讨了聚苯胺的结构（金属配位方式、手性特征等）与催化性能的关系；深入研究了聚苯胺配合物的结构对共聚产物的分子量、分子量分布、链结构的影响；分析了共聚产物结构与其热稳定性、光学性能等性能之间的关系。相关研究结果发表学术论文18篇，SCI收录14篇，EI收录1篇，中文核心3篇。培养博士研究生1名，硕士研究生7名。