Parsons Leo W T, Berben Louise A
Department of Chemistry, University of California Davis CA 95616 USA
Chem Sci. 2023 Jul 17;14(31):8234-8248. doi: 10.1039/d3sc02080k. eCollection 2023 Aug 9.
Hydride transfer (HT) is a fundamental step in a wide range of reaction pathways, including those mediated by dihydropyridinates (DHPs). Coordination of ions directly to the pyridine ring or functional groups stemming therefrom, provides a powerful approach for influencing the electronic structure and in turn HT chemistry. Much of the work in this area is inspired by the chemistry of bioinorganic systems including NADH. Coordination of metal ions to pyridines lowers the electron density in the pyridine ring and lowers the reduction potential: lower-energy reactions and enhanced selectivity are two outcomes from these modifications. Herein, we discuss approaches for the preparation of DHP-metal complexes and selected examples of their reactivity. We suggest further areas in which these metallated DHPs could be developed and applied in synthesis and catalysis.
氢化物转移（HT）是广泛反应途径中的一个基本步骤，包括由二氢吡啶盐（DHP）介导的那些反应途径。离子直接与吡啶环或源于吡啶环的官能团配位，为影响电子结构进而影响HT化学提供了一种有力方法。该领域的许多工作都受到包括NADH在内的生物无机体系化学的启发。金属离子与吡啶配位会降低吡啶环中的电子密度并降低还原电位：这些修饰的两个结果是实现能量更低的反应和更高的选择性。在此，我们讨论制备DHP-金属配合物的方法及其反应活性的选定实例。我们提出了这些金属化DHP在合成和催化中可进一步开发和应用的其他领域。
