We introduce the convergent synthesis of linear monodisperse sequence‐defined oligomers through a unique approach, combining the Passerini three‐component reaction (P‐3CR) and a Diels–Alder (DA) reaction based on photocaged dienes. A set of oligomers is prepared resting on a Passerini linker unit carrying an isocyano group for chain extension by P‐3CR and a maleimide moiety for photoenol conjugation enabling a modular approach for chain growth. Monodisperse oligomers are accessible in a stepwise fashion by switching between both reaction types. Employing sebacic acid as a core unit allows the synthesis of a library of symmetric sequence‐defined oligomers. The oligomers consist of alternating P‐3CR and photoblocks with molecular weights up to 3532.16 g mol⁻¹, demonstrating the successful switching from P‐3CR to photoenol conjugation. In‐depth characterization was carried out including size‐exclusion chromatography (SEC), high‐resolution electrospray ionization mass spectrometry (ESI‐MS) and NMR spectroscopy, evidencing the monodisperse nature of the precision oligomers.

中文翻译：

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结合的光化学和多组分反应方法制备低聚物

我们通过独特的方法介绍了线性单分散序列定义的低聚物的融合合成，该方法结合了Passerini三组分反应（P-3CR）和基于光笼二烯的Diels-Alder（DA）反应。在Passerini连接器单元上准备了一组低聚物，该单元带有一个异氰基以通过P-3CR进行链延伸，并带有一个马来酰亚胺部分进行光烯醇共轭，从而实现了模块化的链增长方法。通过在两种反应类型之间切换，可逐步获得单分散低聚物。使用癸二酸作为核心单元可以合成对称序列定义的低聚物文库。低聚物由交替的P-3CR和分子量高达3532.16 g mol ^-1的光嵌段组成，证明了从P-3CR到光烯醇共轭的成功转换。进行了深入表征，包括尺寸排阻色谱（SEC），高分辨率电喷雾电离质谱（ESI-MS）和NMR光谱，证明了精密低聚物的单分散性。