Konrad Waldemar, Bloesser Fabian R, Wetzel Katharina S, Boukis Andreas C, Meier Michael A R, Barner-Kowollik Christopher
Macromolecular Architectures, Institut für Technische Chemie und Polymerchemie, Karlsruhe Institute of Technology (KIT), Engesserstrasse 18, 76131, Karlsruhe, Germany.
Institut für Biologische Grenzflächen, Karlsruhe Institute of, Technology (KIT), Hermann-von-Helmholtz Platz 1, 76344, Eggenstein-Leopoldshafen, Germany.
Chemistry. 2018 Mar 7;24(14):3413-3419. doi: 10.1002/chem.201705939. Epub 2018 Feb 5.
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 , 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.
我们通过一种独特的方法介绍了线性单分散序列定义的低聚物的收敛合成，该方法结合了帕瑟里尼三组分反应（P-3CR）和基于光笼二烯的狄尔斯-阿尔德（DA）反应。基于带有异氰基的帕瑟里尼连接单元制备了一组低聚物，该连接单元用于通过P-3CR进行链延伸，以及带有马来酰亚胺部分用于光烯醇共轭，从而实现了链增长的模块化方法。通过在两种反应类型之间切换，可以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。这些低聚物由交替的P-3CR和光阻断剂组成，分子量高达3532.16 g/mol，证明了从P-3CR到光烯醇共轭的成功切换。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）和核磁共振光谱，证明了精密低聚物的单分散性质。
