摘要/Abstract
亚砜类化合物在有机合成和药物化学中有着广泛的应用, 手性亚砜作为助剂、配体、催化剂和合成子的用途已得到充分证明, 亚砜类化合物的亚磺酰基团也可作为药效团、羰基生物等排体或药物分子修饰基团应用于药物设计和药物开发之中. 综述了具有生物活性的亚砜类化合物的结构骨架以及相应的作用机制, 并总结了近十年来通过构建硫立体中心制备手性亚砜类化合物的新方法和新进展, 具体到廉价金属铁络合物、多金属氧酸盐、有机小分子、生物酶和电化学催化的硫醚不对称氧化反应, 以及基于次磺酸阴离子中间体的手性亚砜合成策略和最近涌现的新策略, 其中也包括作者最近在手性亚砜合成领域取得一些研究成果.
关键词: 亚砜生物活性分子, 亚砜药物, 不对称合成, 硫醚氧化反应, 次磺酸阴离子, 多金属氧酸盐
Sulfoxide compounds bearing unique sulfinyl group have attracted extensive attentions due to their important application in asymmetric organic synthesis and medicinal chemistry. The utility of chiral sulfoxides as versatile auxiliaries, ligands, and catalysts and synthons has been well demonstrated. Furthermore, the sulfinyl moiety can act as a pharmaceutical core, a bioisosteric replacement of the carbonyl moiety or a modifier in drug design and drug development. In this review, their biological activities with esomeprazole, ajoene, sulforaphane, sulforaphene, cenicriviroc, arbidol sulfoxide, armodafinil and so on are exemplified. And their mechanisms of action are illustrated briefly. Since the sulfur chirality is different from carbon stereogenic center, much effort has been devoted to the preparation of chiral sulfoxides. Herein the advances in asymmetric synthesis of sulfoxide during the past decade are presented. The direct asymmetric oxidation of prochiral sulfides with cheap iron-complex catalyst, polyoxometalates, organocatalyst, biocatalyst and electrocatalyst is discussed. Moreover, the complementary strategy based on sulfenate anions and miscellaneous strategies emerged recently are described. Additionally, our recent research works in the construction of chiral sulfoxide are also mentioned.
Key words: bioactive sulfoxide, sulfoxide drug, asymmetric synthesis, sulfoxidation, sulfenate anion, polyoxometalates
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