Biomimetic Diels–Alder Reactions in Natural Product Synthesis: A Personal Retrospect

Abstract

Nature has been recognized for her super capability of constructing complex molecules with remarkable efficiency and elegancy. Among nature’s versatile synthetic toolkits, Diels-Alder reaction is particularly attractive since it allows for rapid generation of molecular complexity from simple precursors. For natural products biosynthetically formed through Diels-Alder reactions, the most straightforward way to access them should build on biomimetic Diels-Alder reactions. However, the implementation of biomimetic Diels-Alder reactions in a laboratory setting may encounter considerable challenges, particularly for those suffering from complicated reactivity and selectivity issues. Indeed, the translation of a biosynthetic hypothesis into a real biomimetic synthesis entails the orchestrated combination of nature’s inspiration and chemist’s rational design. In this account, we will briefly summarize our recent progress on the application of biomimetic Diels-Alder reactions in natural product synthesis. As shown in the discussed stories, rational manipulation of the structures of biosynthetic precursors plays a crucial role for the successful implementation of biomimetic Diels-Alder reactions. 1 Introduction 2 Biomimetic Synthesis of Rossinone B 3 Biomimetic Synthesis of Homodimericin A 4 Biomimetic Synthesis of Polycyclic and Dimeric Xanthanolides 5 Biomimetic Synthesis of Periconiasins and Pericoannosins 6 Biomimetic Synthesis of Merocyctochalasans 7 Conclusion and outlook