Kalvet Indrek, Deckers Kristina, Funes-Ardoiz Ignacio, Magnin Guillaume, Sperger Theresa, Kremer Marius, Schoenebeck Franziska
Institute of Organic Chemistry, RWTH Aachen University, Landoltweg 1, 52074, Aachen, Germany.
Angew Chem Int Ed Engl. 2020 May 11;59(20):7721-7725. doi: 10.1002/anie.202001326. Epub 2020 Mar 17.
Contrary to the general belief that Pd-catalyzed cross-coupling at sites of severe steric hindrance are disfavored, we herein show that the oxidative addition to C-Br ortho to an adamantyl group is as favored as the corresponding adamantyl-free system due to attractive dispersion forces. This enabled the development of a fully selective arylation and alkylation of C-Br ortho to an adamantyl group, even if challenged with competing non-hindered C-OTf or C-Cl sites. The method makes use of an air-stable Pd dimer and enables straightforward access to diversely substituted therapeutically important adamantylarenes in 5-30 min.
与普遍认为钯催化在严重空间位阻位点的交叉偶联不利的观点相反，我们在此表明，由于存在有吸引力的色散力，向金刚烷基邻位的C-Br进行氧化加成与相应的无金刚烷基体系一样有利。这使得能够开发出对金刚烷基邻位的C-Br进行完全选择性的芳基化和烷基化反应，即使存在竞争性的无位阻C-OTf或C-Cl位点的挑战。该方法使用了一种空气稳定的钯二聚体，能够在5-30分钟内直接获得多种取代的具有治疗重要性的金刚烷基芳烃。
