氧杂环丁烷的合成

Synthesis of Oxetanes

氧杂环丁烷作为一类饱和四元环醚类化合物,不仅是重要的有机合成中间体,也是天然和合成的具有抗癌、抗HIV、抑制谷氨酰胺合成酶等多种生物或药物活性化合物分子结构中的重要活性单元。因此,发展氧杂环丁烷骨架的有效合成方法非常重要。本文以分子内形成C—C键的环化反应、分子内形成C—O键的Williamson醚化反应、烯烃和醛酮[2+2]光环加成反应(Paternò-Büchi反应)、过渡金属催化的形式[2+2]环加成反应、硫叶立德介导的环氧乙烷扩环反应和C—H键氧化环化反应等方面较系统综述了近5年内关于氧杂环丁烷合成方法的新进展。希望本文能为致力于发展构建氧杂环丁烷骨架的有机合成化学家提供一些有价值的信息,以便促进氧杂环丁烷合成方法的发展及应用。

Oxetanes are a class of saturated four-membered cyclic ether compounds.They are not only an important class of organic synthetic intermediates,but also crucial active structural units of natural and synthetic biological and medicinal active compounds possessing anti-cancer,inhibition of human immunodeficiency virus,as well as inhibiting glutamine synthetase in clinical practice.Thus,it is in high demand to develop efficient methods for constructing oxetane structural motifs.In this review,the intramolecular cyclization reaction via C—C bond formation,the intramolecular Williamson etherification by the formation of C—O bond,the[2+2]photocycloadditions of alkenes with aldehydes and ketones(named as Paternò-Büchi reaction),transition metal catalyzed formal[2+2]cycloadditions,sulfide ylide-mediated epoxide ring expansion,and the C—H bond oxidative cyclization are reviewed with a focus on new progress in the synthesis of oxetanes during the last five years.It is hoped that this review can provide some valuable information for the organic chemists who are interested in the construction of the oxetane skeleton and promote the development on the synthesis and application of oxetanes.