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

Key words

Diels–Alder reaction - natural product - biomimetic synthesis - reactivity - selectivity

Publication History

Received: 31 December 2021

Accepted after revision: 22 January 2022

Accepted Manuscript online:
22 January 2022

Article published online:
28 February 2022

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