基于三氟甲基砌块的催化不对称傅-克反应研究进展

doi:10.6023/A13010078

摘要/Abstract

引入三氟甲基基团可以显著提高有机分子的化学和代谢稳定性、亲脂性以及在细胞膜中的渗透性, 因此发展高效合成三氟甲基化合物, 特别是手性三氟甲基化合物的方法具有非常重要的意义. 基于三氟甲基砌块的催化不对称傅-克反应可以高效高选择性获得手性三氟甲基芳香化合物, 是最近发展起来的一个研究热点. 自从日本Mikami小组采用手性钛络合物研究了首例基于三氟甲基砌块的催化不对称傅-克反应, 不同种类的手性有机金属催化剂(如手性钛, 铜, 锌, 锆, 钯, 镱, 钇, 镍, 钙等金属络合物)和手性有机小分子催化剂(如金鸡纳碱, 手性脯氨醇硅醚, 手性磷酸等)都在这类不对称催化反应中得到应用. 作者主要对反应组分(特别是不同类型的三氟甲基砌块)、反应条件、反应机理和合成应用等方面的研究进行了综述. 最后, 对这类反应所存在的问题和局限性进行了总结, 并对今后发展方向作了展望.

关键词: 不对称催化, 傅-克反应, 不对称合成, 三氟甲基, 手性

The incorporation of a trifluoromethyl (CF₃) group can increase chemical and metabolic stability, lipophilicity, and membrane permeability of the molecules. As a consequence, the exploitation of efficient methods to construct chiral trifluoromethylated compounds is a highly significant task. Two strategies are often utilized to synthesize compounds bearing a CF₃ group at the chiral center. The first strategy is the transfer of a CF₃ group from a reagent. This strategy seems to be straightforward and practical, but direct enantioselective trifluoromethylation remains a challenge, and high enantioselectivities are rarely reached. An alternative strategy is the application of some established asymmetric catalytic reactions by using trifluoromethylated compounds as building blocks, which could provide various chiral trifluoromethylated products in high yields and enantioselectivities under mild conditions. Asymmetric Friedel-Crafts reaction has witnessed rapid development in recent years. Asymmetric Friedel-Crafts reaction using prochiral trifluoromethylated starting materials represents an important method for the access of trifluoromethylated derivatives of chiral aromatic compounds. Since Mikami's group identified that chiral BINOL-derived Ti(IV) complexs could be applied in the asymmetric Friedel-Crafts reaction with fluoral to obtain chiral trifluoromethylated compounds, considerable efforts have been dedicated to utilize other chiral organometallic catalysts (such as chiral Ti, Cu, Zn, Zr, Pd, Y, Yb, Ni, Ca complex, etc.) and chiral organo-catalysts (such as cinchona alkaloids, chiral prolinol ethers, chiral phosphoric acids, etc.) in this type of catalytic reaction. Chiral trifluoromethylated compounds with a CF₃-group at a chiral carbon center with, or without any heteroatom substituents were obtained in high yields and enantioselectivities. The components (especially CF₃-containing starting material of trifluoromethyl ketones, imines and olefins), conditions and mechanism of the Friedel-Crafts reactions, and the synthetic utilities of Friedel-Crafts adducts are discussed in this review. Finally, the existing problem and limitation of this Friedel-Crafts reaction are summarized, and the key prospect of the chiral CF₃-containing product-driven Friedel-Crafts reaction is also described. The aim of this review is to stimulate further developments in this area.

Key words: asymmetric catalysis, Friedel-Crafts reaction, asymmetric synthesis, trifluoromethylated, chiral

引用此文

何展荣, 黄毅勇, Verpoort Francis. 基于三氟甲基砌块的催化不对称傅-克反应研究进展[J]. 化学学报, 2013, 71(05): 700-712.

He hanrong, Huang Yiyong, Verpoort Francis. Recent Advances in Catalytic Asymmetric Friedel-Crafts Reactions with Prochiral Trifluoromethylated Compounds[J]. Acta Chimica Sinica, 2013, 71(05): 700-712.

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