Yang Jenny Y, King Ryan P
Department of Chemistry, University of California, Irvine, Irvine, California 92697-2025, United States.
ACS Org Inorg Au. 2024 Jul 17;4(5):526-533. doi: 10.1021/acsorginorgau.4c00031. eCollection 2024 Oct 2.
Bipyridines and azaarenes are an important class of ligands that impart unique and tunable properties to transition metal complexes and catalysts. While some derivatives are commercially available, noncommercial analogues are often challenging to prepare and purify. Herein, we report a general nucleophilic aromatic substitution reaction that converts cationic trimethylaminated bipyridines into a series of functionalized bipyridines. Our method showcases a series of C-O, C-S, and C-F bond-forming reactions as well as a selective monodemethylation that converts the electron-deficient trimethylammonium to an electron-rich dimethylamine. The approach was further applied to diversification of pharmaceuticals and natural products and was applied to the total synthesis of Graveolinine and the preparation of Graveolinine derivatives.
联吡啶和氮杂芳烃是一类重要的配体，能赋予过渡金属配合物和催化剂独特且可调节的性质。虽然一些衍生物有商业供应，但非商业类似物的制备和纯化往往具有挑战性。在此，我们报道了一种通用的亲核芳香取代反应，该反应可将阳离子型三甲基胺化联吡啶转化为一系列功能化联吡啶。我们的方法展示了一系列形成C-O、C-S和C-F键的反应以及一种选择性单脱甲基反应，该反应将缺电子的三甲基铵转化为富电子的二甲胺。该方法进一步应用于药物和天然产物的多样化合成，并应用于Graveolinine的全合成及Graveolinine衍生物的制备。
