Natural product synthesis remains one of the most vibrant and intellectually rewarding areas of chemistry, although the justifications for pursuing it have evolved over time. In the early years, the emphasis lay on structure elucidation and confirmation through synthesis, as exemplified by celebrated studies on cocaine, morphine, strychnine and chlorophyll. This was followed by a phase where the sheer demonstration that highly complex molecules could be recreated in the laboratory in a rational manner was enough to justify the economic expense and intellectual agonies of a synthesis. Since then, syntheses of natural products have served as platforms for the demonstration of elegant strategies, for inventing new methodology ‘on the fly’ or to demonstrate the usefulness and scope of methods established with simpler molecules. We now add another aspect that we find fascinating, viz. ‘natural product anticipation’. In this Review, we survey cases where the synthesis of a compound in the laboratory has preceded its isolation from nature. The focus of our Review lies on examples where this anticipation of a natural product has triggered a successful search or where synthesis and isolation have occurred independently. Finally, we highlight cases where a potential natural product structure has been suggested as a result of synthetic endeavours but not yet confirmed by isolation, inviting further collaborations between synthetic and natural product chemists.

天然产物合成仍然是化学中最具活力和智力回报的领域之一，尽管追求它的理由随着时间的推移而不断变化。早年的重点是通过合成进行结构阐明和确认，对可卡因、吗啡、士的宁和叶绿素的著名研究就是例证。接下来的一个阶段是，纯粹的证明高度复杂的分子可以在实验室中以合理的方式重新创建，这足以证明合成的经济费用和智力上的痛苦是合理的。从那时起，天然产物的合成就成为展示优雅策略、“即时”发明新方法或展示用更简单分子建立的方法的有用性和范围的平台。我们现在添加另一个我们觉得有趣的方面，即。 “天然产品预期”。在这篇综述中，我们调查了在实验室中合成化合物先于从自然界中分离出来的案例。我们评论的重点在于对天然产物的预期引发了成功的搜索或合成和分离独立发生的例子。最后，我们重点介绍了通过合成努力提出潜在天然产物结构但尚未通过分离证实的情况，邀请合成和天然产物化学家之间进一步合作。