项目名称: 金属-有机骨架化合物(MOFs)的手性后合成修饰及不对称催化研究
项目编号: No.21261017
项目类型: 地区科学基金项目
立项/批准年度: 2013
项目学科: 数理科学和化学
项目作者: 陈超
作者单位: 南昌大学
项目金额: 48万元
中文摘要: 作为手性底物,手性金属-有机骨架化合物(MOFs)具有较大比表面积、有序的孔道结构和良好的主-客体适应能力,在手性有机分子的对映体拆分、择形催化、选择性吸附等方面表现出巨大的应用潜能。但是,由于MOFs晶体工程学合成理论仍不完善,很难根据实际需要设计合成出适合手性催化反应的MOFs手性孔道。本课题欲采用后合成修饰技术(Postsynthetic Modification)将手性活性分子(如手性酒石酸、脯氨酸衍生物)锚接在不同孔道类型的MOFs上。根据手性催化反应特点,采用分子动力学的方法分别对手性催化反应前后分子的构型特点,后合成修饰后的MOFs的孔道大小及对催化反应分子的结构匹配性进行模拟计算,设计、筛选出最优固体微孔催化剂,以Sharpless不对称环氧化、手性羟醛缩合等反应对其进行手性催化评估。最后探索结构-产率-立体选择性之间的关系,积累相关数据,为我国不对称催化研究开辟新的途径。
中文关键词: 金属-有机骨架化合物;手性;后合成修饰;不对称催化;
英文摘要: Many advantages of chiral metal-organic framework (MOFs) such as high surface areas, uniform pores and chemical tunability make these materials invaluable for chiral separation and heterogeneous asymmetric catalysis. However, rational design and synthesis of chiral MOFs for certain asymmetric catalytic reactions are still long-standing challenge due to the faultiness of crystal engineering theory. In this project, a series of organic chiral molecules with high efficiently catalytic activities such as tartaric acid and proline would be incorporated and anchored in the channel of MOFs by means of postsynthetic modification (PSM) and molecular dynamics simulation technologies. We hope the introduced catalytic centers and chiral induction sites by PSM strategy could be in close proximity with proper relative orientation to achieve strong asymmetric induction, resulting in high enantioselectivity in MOFs. The as-synthesized catalysts would be evaluated by Sharpless enantioselective epoxidation and asymmetric aldol condensation reactions, and the catalysis mechanism and relationship between syntheses and structures also would be surveyed.
英文关键词: Metal-organic frameworks;Chiral;Post-synthetic modification;asymmetric catalysis;