Marchese Austin D, Lind Florian, Mahon Áine E, Yoon Hyung, Lautens Mark
Davenport Research Laboratories, Department of Chemistry, University of Toronto, 80 St. George Street, Toronto, Ontario, M5S 3H6, Canada.
Angew Chem Int Ed Engl. 2019 Apr 1;58(15):5095-5099. doi: 10.1002/anie.201900659. Epub 2019 Mar 12.
A diastereoselective dearomative carboiodination reaction is reported. We report a novel metal-catalyzed approach to install reactive secondary benzylic iodides. Utilizing the unique reactivity of nickel, we have expanded the carboiodination reaction to non-activated aromatic double bonds forming a previously unattainable class of iodides. We also report a broadly applicable method to avoid the use of a metallic reducing agent by utilizing an alkyl phosphite as the ligand. The reaction is thought to proceed through a syn intramolecular carbonickelation across a 2-substituted indole followed by a diastereoretentive reductive elimination of the carbon-iodine bond. The complex iodinated indolines generated in the reaction were obtained in moderate to good yields and good to excellent diastereoselectivity. The products were easily functionalized by a variety of synthetic methods.
报道了一种非对映选择性的去芳构化碳碘化反应。我们报道了一种用于安装活性仲苄基碘化物的新型金属催化方法。利用镍的独特反应性，我们将碳碘化反应扩展到未活化的芳族双键，形成了一类以前无法获得的碘化物。我们还报道了一种广泛适用的方法，通过使用亚磷酸烷基酯作为配体来避免使用金属还原剂。该反应被认为是通过2-取代吲哚上的分子内顺式碳镍化，然后进行碳-碘键的非对映保持还原消除来进行的。反应中生成的复杂碘化二氢吲哚以中等至良好的产率和良好至优异的非对映选择性得到。产物可通过多种合成方法轻松官能化。
