Catalytic Asymmetric Synthesis of Fluorine-containing Substrates (Flustrates)

本工作的目的是在催化不对称羰基烯、醛醇和Diels-Alder与前手性氟、二氟乙醛等反应的基础上，建立催化不对称合成含氟底物（氟化合物）的方法。主要研究结果如下：(1)催化烯与氟的不对称反应羰基烯与氟的不对称反应通过手性双萘酚衍生钛配合物的不对称催化，使红-三氟甲基甲醇的对映选择性达到90%以上。(2)催化不对称醛醇与氟的反应Mukaiyama醛醇与氟和二氟乙醛的反应发现，手性双萘酚衍生的钛配合物的不对称催化使含氟醛醇产物的对映选择性超过90%。(3)催化Diels-Alder与氟的不对称反应迄今为止，即使是手性修饰的双萘酚衍生钛配合物也无法催化Diels-Alder与氟的不对称反应。

The purpose of this work is to develop the method for catalytic asymmetric synthesis of fluorine-containing substrates (flustrates) based on catalytic asymmetric carbonyl-ene, aldol, and Diels-Alder reactions with prochiral fluoral, difluoroacetaldehyde, and so forth. A summary of the research results is as follow :(1) Catalytic Asymmetric Ene Reaction with FluoralThe carbonyl-ene reaction with fluoral is found to afford the erythro-trifluoromethylcarbinol in more than 90% enantioselectivity by the asymmetric catalysis of chiral binaphthol-derived titanium complexes.(2) Catalytic Asymmetric Aldol Reaction with FluoralThe Mukaiyama aldol reaction with fluoral and difluoroacetaldehyde is found to afford the fluorine containing aldol products in more than 90% enantioselectivity by the asymmetric catalysis of chiral binaphthol-derived titanium complexes.(3) Catalytic Asymmetric Diels-Alder Reaction with FluoralThe asymmetric catalysis of Diels-Alder reaction with fluoral is so far unsuccessful even by the catalysis of chiral modified binaphthol-derived titanium complexes.