Department of Chemistry and Biomolecular Science, University of Ottawa, 10 Marie Curie, Ottawa, Ontario K1N 6N5, Canada.
Chem Rev. 2021 Jun 23;121(12):6699-6717. doi: 10.1021/acs.chemrev.0c00832. Epub 2021 Jan 19.
Bioorthogonal chemical reactions have emerged as convenient and rapid methods for incorporating unnatural functionality into living systems. Different prototype reactions have been optimized for use in biological settings. Optimization of 3 + 2 dipolar cycloadditions involving nitrones has resulted in highly efficient reaction conditions for bioorthogonal chemistry. Through substitution at the nitrone carbon or nitrogen atom, stereoelectronic tuning of the reactivity of the dipole has assisted in optimizing reactivity. Nitrones have been shown to react rapidly with cyclooctynes with bimolecular rate constants approaching = 10 M s, which are among the fastest bioorthogonal reactions reported (McKay et al. , , 3066-3070). Nitrones have also been shown to react with -cyclooctenes (TCO) in strain-promoted TCO-nitrone cycloadditions reactions. Copper catalyzed reactions involving alkynes and nitrones have also been optimized for applications in biology. This review provides a comprehensive accounting of the different bioorthogonal reactions that have been developed using nitrones as versatile reactants, and provides some recent examples of applications for probing biological systems.
生物正交化学反应已成为向活系统中引入非天然官能团的便捷、快速方法。不同的原型反应已被优化用于生物环境。通过优化涉及硝酮的 3 + 2 偶极环加成反应，已经为生物正交化学产生了高效的反应条件。通过硝酮碳或氮原子的取代，立体电子对反应性的调整有助于优化反应性。硝酮已被证明可与环辛炔快速反应，双分子速率常数接近 = 10 M s ，这是报道的最快的生物正交反应之一（McKay 等人，，3066-3070）。硝酮也已被证明可与 -环辛烯（TCO）在应变促进的 TCO-硝酮环加成反应中反应。涉及炔烃和硝酮的铜催化反应也已被优化，以应用于生物学。这篇综述全面介绍了使用硝酮作为多功能反应物开发的不同生物正交反应，并提供了一些最近用于探测生物系统的应用实例。
