School of Chemistry, University of Birmingham, Edgbaston, Birmingham B15 2TT, U.K.
Chem Rev. 2021 Jun 23;121(12):6744-6776. doi: 10.1021/acs.chemrev.0c01076. Epub 2021 Mar 25.
The 1,4-conjugate addition reaction between activated alkynes or acetylenic Michael acceptors and nucleophiles (, the nucleophilic Michael reaction) is a historically useful organic transformation. Despite its general utility, the efficiency and outcomes can vary widely and are often closely dependent upon specific reaction conditions. Nevertheless, with improvements in reaction design, including catalyst development and an expansion of the substrate scope to feature more electrophilic alkynes, many examples now present with features that are congruent with Click chemistry. Although several nucleophilic species can participate in these conjugate additions, ubiquitous nucleophiles such as thiols, amines, and alcohols are commonly employed and, consequently, among the most well developed. For many years, these conjugate additions were largely relegated to organic chemistry, but in the last few decades their use has expanded into other spheres such as bioorganic chemistry and polymer chemistry. Within these fields, they have been particularly useful for bioconjugation reactions and step-growth polymerizations, respectively, due to their excellent efficiency, orthogonality, and ambient reactivity. The reaction is expected to feature in increasingly divergent application settings as it continues to emerge as a Click reaction.
1,4-共轭加成反应是一种在历史上具有重要作用的有机转化反应，它发生在活化的炔烃或乙酰基迈克尔受体与亲核试剂（即亲核迈克尔反应）之间。尽管该反应具有广泛的通用性，但反应的效率和结果可能会有很大的差异，并且通常密切依赖于特定的反应条件。然而，通过改进反应设计，包括催化剂的开发以及扩大底物范围以包含更多亲电性的炔烃，许多反应现在都具有与点击化学一致的特征。尽管有几种亲核试剂可以参与这些共轭加成反应，但普遍存在的亲核试剂，如硫醇、胺和醇，通常被广泛使用，因此它们是发展最为成熟的亲核试剂之一。多年来，这些共轭加成反应主要局限于有机化学领域，但在过去几十年中，其应用范围已经扩展到生物有机化学和聚合物化学等其他领域。在这些领域中，由于其具有极好的效率、正交性和环境反应性，它们在生物偶联反应和逐步聚合反应中特别有用。随着它继续作为一种点击反应出现，该反应预计将在越来越多不同的应用场景中得到应用。
