Miró Javier, Sánchez-Roselló María, González Javier, del Pozo Carlos, Fustero Santos
Departamento de Química Orgánica, Universidad de Valencia, 46100 Burjassot (Spain).
Chemistry. 2015 Mar 27;21(14):5459-66. doi: 10.1002/chem.201406224. Epub 2015 Feb 20.
A tandem gold-catalyzed hydroamination/formal aza-Diels-Alder reaction is described. This process, which employs quaternary homopropargyl amino ester substrates, leads to the formation of an intrincate tetracyclic framework and involves the generation of four bonds and five stereocenters in a highly diastereoselective manner. Theoretical calculations have allowed us to propose a suitable mechanistic rationalization for the tandem protocol. Additionally, by studying the influence of the ligands on the rate of the gold-catalyzed reactions, it was possible to establish optimum conditions in which to perform the process with a variety of substituents on the amino ester substrates. Notably, the asymmetric version of the tandem reaction was also evaluated.
描述了一种串联金催化的氢胺化/形式氮杂狄尔斯-阿尔德反应。该过程采用季铵型高炔丙基氨基酯底物，导致形成复杂的四环骨架，并以高度非对映选择性的方式生成四个键和五个立体中心。理论计算使我们能够为串联反应方案提出合适的机理解释。此外，通过研究配体对金催化反应速率的影响，有可能确定在氨基酯底物上带有各种取代基时进行该过程的最佳条件。值得注意的是，还评估了串联反应的不对称形式。
