Polycyclic scaffolds are omnipresent in natural products and drugs, and the synthetic strategies and methods toward construction of these scaffolds are of particular importance. Compared to simple cyclic ring systems, polycyclic scaffolds have higher structure complexity and diversity, making them suitable for charting broader chemical space, yet bringing challenges for the syntheses. In this review, we surveyed progress in the past decade on synthetic methods for polycyclic natural product scaffolds, in which the key steps are one-pot reactions involving intermolecular or intramolecular alkyne annulation. Synthetic strategies of selected polycyclic carbocycles and heterocycles with at least three fused, bridged, or spiro rings are discussed with emphasis on the synthetic efficiency and product diversity. Recent examples containing newly developed synthetic concepts or toolkits such as collective and divergent total synthesis, gold catalysis, C–H functionalization, and dearomative cyclization are highlighted. Finally, several “privileged synthetic strategies” for “privileged polycyclic scaffolds” are summarized, with discussion of remained challenges and future perspectives.

多环支架在天然产物和药物中无处不在，并且构建这些支架的合成策略和方法特别重要。与简单的环系统相比，多环支架具有更高的结构复杂性和多样性，使其适用于绘制更广阔的化学空间，但也给合成带来了挑战。在这篇综述中，我们调查了过去十年中多环天然产物支架合成方法的进展，其中关键步骤是涉及分子间或分子内炔烃环合反应的一锅法反应。讨论了具有至少三个稠环，桥环或螺环的所选多环碳环和杂环的合成策略，重点是合成效率和产品多样性。重点介绍了包含新近开发的合成概念或工具包的最新示例，例如集体和发散的总合成，金催化，CH功能化和脱芳香环化。最后，总结了“特权多环支架”的几种“特权合成策略”，并讨论了仍然存在的挑战和未来前景。