Cylindrocyclophanes are a class of naturally occurring 22-membered macrocycles with a unique architecture and interesting physical, chemical, and biological properties. This comprehensive account summarizes progress in various synthetic approaches to these compounds during the last twenty years, thereby emphasizing the key steps for establishing the [7,7]-paracyclophane scaffold, as well as alternative approaches to the construction of its stereocenters. Many of these syntheses highlight the power of transition-metal catalysis for natural-product synthesis. Furthermore, the unraveling of the biosynthesis to these natural products in Cylindrospermum licheniforme is discussed. 1 Introduction 2 Biosynthesis 3 Smith’s Synthesis of (–)-Cylindrocyclophanes A and F 4 Hoye’s Synthesis of (–)-Cylindrocyclophane A 5 Iwabuchi’s Syntheses of (–)-Cylindrocyclophane A and (+)-Cylindrocyclophane A 6 Nicolaou’s Synthesis of (–)-Cylindrocyclophanes A and F 7 Breit’s Synthesis of (–)-Cylindrocyclophane F 8 Conclusion

中文翻译：

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环环芳烃的全合成证明了过渡金属催化在天然产物合成中的作用

Cylindrocyclophanes 是一类天然存在的 22 元大环化合物，具有独特的结构和有趣的物理、化学和生物特性。这篇综合报道总结了过去二十年这些化合物的各种合成方法的进展，从而强调了建立 [7,7]-对环芳烃支架的关键步骤，以及构建其立体中心的替代方法。其中许多合成突出了过渡金属催化天然产物合成的能力。此外，还讨论了在 Cylindrospermum licheniforme 中生物合成这些天然产物的过程。