近日，四川大学钮大文团队研究了钯/光氧化还原催化糖缀合的三组分偶联。这一研究成果于2026年4月14日发表在《德国应用化学》杂志上。

糖基化——即将糖基部分安装到分子靶标上——是一种调控生物功能的强大策略，然而糖基供体和苷元受体固有的结构复杂性长期以来使这一工作面临巨大的合成挑战。尽管Pd催化的烯丙基取代反应被广泛用于构建复杂骨架，但其在糖基化中的应用仍十分罕见。

研究组报道了一种可见光驱动的Pd(0)催化的三组分偶联反应，能够组装结构精细的糖复合物。该方案使用易于获取、对空气稳定的邻碘联苯基硫苷作为糖基供体，并通过糖基自由基中间体进行反应。Pd(0)催化剂发挥双重作用：一方面从硫苷中释放出糖基自由基，另一方面将这些自由基与1,3-丁二烯一起转化为闭壳层的烯丙基-Pd亲电体。这些烯丙基-Pd络合物被多种亲核试剂捕获，即可得到相应的糖复合物。该转化展示了将Pd催化烯丙基取代应用于糖基化的策略，具有广泛的官能团兼容性，并能够实现寡肽和生物活性小分子的后期修饰。实验研究为反应机理提供了深入见解，并阐明了糖基自由基的生成来源。

附：英文原文

Title: Palladium/Photoredox-Catalyzed Three-Component Coupling for Glycoconjugation

Author: Lifan Deng, Ao Shen, Siyu Zhang, Yingwei Wang, Xia Zhang, Dawen Niu

Issue&Volume: 2026-04-14

Abstract: Glycoconjugation—the installation of sugar moieties onto molecular targets—represents a powerful strategy for modulating biological functions, yet the intrinsic structural intricacy of both carbohydrate donors and aglycone acceptors has long rendered this endeavor a formidable synthetic hurdle. Although the Pd-catalyzed allylic substitution is widely exploited to build complex frameworks, its use in glycoconjugation remains scarce. Here we disclose a visible-light-driven, Pd(0)-catalyzed, three-component coupling that assembles elaborate glycoconjugates. The protocol employs readily accessible, bench-stable ortho-iodobiphenyl S-glycosides as glycosyl donors, and proceeds through glycosyl radical intermediates. The Pd(0) catalyst serves dual roles: it liberates glycosyl radicals from the S-glycosides and converts these radicals, together with 1,3-butadiene, into closed-shell allyl-Pd electrophiles. Capture of these allyl-Pd complexes by diverse nucleophiles delivers the corresponding glycoconjugates. The transformation, showcasing a strategy to deploy the Pd-catalyzed allylic substitution in glycoconjugation, exhibits broad functional-group compatibility and enables late-stage modification of oligopeptides and bioactive small molecules. Experimental studies provide insights into the reaction mechanism and elucidate the origin of glycosyl radicals.

DOI: 10.1002/anie.5026514

Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.5026514