Cross‐coupling technology is still the cornerstone of conjugated polymer synthesis. However, most cross‐coupling reactions rely on platinum group metals (e. g. rhodium, palladium, iridium and platinum), and the supply of these rare and expensive metal catalysts is at risk, making the use of these reactions unsustainable. In addition, the contamination of conjugated polymers with trace metallic catalysts is another concern, especially for organic electronics where the products are used in devices whose performance can be affected by even ′undetectable’ levels of metal contaminant. In pursuit of more sustainable chemistry in the future, various organic reactions have been utilized for the synthesis of conjugated polymers without the aid of transition‐metal catalysts. Presented herein is a comprehensive overview of organic reactions for the synthesis of conjugated polymers that go beyond transition metal‐catalysed cross‐coupling reactions. We discuss metal‐free synthesis strategies and methods in detail and divide them into “condensation” reactions, “click” reactions and other miscellaneous reactions. Reaction mechanisms and key intermediates are also elucidated. The aim is to provide researchers and practitioners with valuable insights that will enable them to innovate and expand the horizons of conjugated polymer synthesis.

中文翻译：

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共轭聚合物制备的现代方法：无过渡金属合成的概念


交叉偶联技术仍然是共轭聚合物合成的基石。然而，大多数交叉偶联反应都依赖于铂族金属（例如铑、钯、铱和铂），并且这些稀有且昂贵的金属催化剂的供应面临风险，这使得这些反应的使用不可持续。此外，痕量金属催化剂的共轭聚合物的污染是另一个问题，特别是对于有机电子产品，这些产品用于性能甚至可能受到“无法检测”水平的金属污染物影响的设备。为了追求未来更可持续的化学，各种有机反应已被用于合成共轭聚合物，而无需过渡金属催化剂的帮助。本文全面概述了用于合成共轭聚合物的有机反应，这些反应超越了过渡金属催化的交叉偶联反应。我们详细讨论了无金属合成策略和方法，并将它们分为“缩合”反应、“点击”反应和其他杂项反应。还阐明了反应机制和关键中间体。其目的是为研究人员和从业者提供有价值的见解，使他们能够创新和扩大共轭聚合物合成的视野。