Vinyl Sulfonates: A Click Function for Coupling-and-Decoupling Chemistry and their Applications
Vinyl Sulfonates: A Click Function for Coupling-and-Decoupling Chemistry and their Applications
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DOI：
10.1002/adsc.201600628
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发表时间：
2016-11-03
影响因子：
5.4
通讯作者：
Santoyo-Gonzalez, Francisco
中科院分区：
文献类型：
--
作者：
Cruz, Carlos M.;Ortega-Munoz, Mariano;Santoyo-Gonzalez, Francisco
术语偶联和去偶联（CAD）化学是指其中需要两个部分之间的有效键形成和随后的裂解的应用。在此背景下，乙烯基磺酸盐（VSO）组作为CAD化学的有效工具的范围进行了报道。偶联步骤依赖于不同亲核试剂对乙烯基磺酸酯的迈克尔型加成的点击特征作为有价值的方法。该策略的可行性已被证明在温和的条件下与模型VSO衍生物获得的高产率。通过与不同亲核试剂的亲核取代（对于烷基VSO基团）或通过水解（对于烷基和芳基VSO）裂解所得磺酸盐加合物是用于解耦步骤的成功策略，前者是最有希望的，因为反应在较温和的条件下与硫醇亲核试剂进行。此外，点击VSO偶联化学被证明与点击CuAAC反应正交，这使得VSO-CAD方法能够用于制备用于双击模块化策略的异双功能可点击和可切割接头。VSO-CAD化学的潜力在两个生物学相关的例子中得到了证明：在与生命系统相容的条件下，磺酸盐与谷胱甘肽（GSH）的解耦;以及从1-硫代和1-叠氮基或1-叠氮基乙基糖衍生物和双乙烯基磺酸酯（同系）或炔基-VSO双官能可点击-可裂解接头（异系）合成同系和异系多价糖基化体系。作为概念的证明，这些多价系统的可裂解特性通过使用它们中的一个作为两种模型凝集素的非共价组装和化学解耦的可逆接头来证明。
The term coupling-and-decoupling (CAD) chemistry refers to applications in which efficient bond formation and subsequent cleavage between two moieties is required. Within this context, the scope of the vinyl sulfonate (VSO) group as an efficient tool for CAD chemistry is reported. The coupling step relies on the click features of the Michael-type addition of diverse nucleophiles to vinyl sulfonates as a valuable methodology. The feasibility of this strategy has been proved by the high yields obtained in mild conditions with model VSO derivatives. Cleavage of the resulting sulfonate adducts either through nucleophilic substitution with different nucleophiles (for alkyl VSO groups) or through hydrolysis (for both alkyl and aryl VSO) are successful strategies for the decoupling step, the former being the most promising, as the reaction proceeds under milder conditions with thiol nucleophiles. Moreover, the click VSO coupling chemistry proves to be orthogonal with the click CuAAC reaction, which enables the VSO-CAD methodology for the preparation of hetero-bifunctional clickable and cleavable linkers for double click modular strategies. The potential of the VSO-CAD chemistry is demonstrated in two biologically relevant examples: the decoupling of sulfonates with glutathione (GSH) under conditions compatible with those of living systems; and the synthesis of homo-and heterogeneous multivalent glycosylated systems from 1-thio and 1-azido or 1-azidoethyl sugar derivatives and bis-vinyl sulfonates (homo systems) or alkynyl-VSO bifunctional clickable-cleavable linkers (hetero systems). As proof of concept, the cleavable character of these multivalent systems was demonstrated by using one of them as a reversible linker for the non-covalent assembling and chemical decoupling of two model lectins.