Rodríguez-Nuévalos Silvia, Espinosa Miguel, Leyva-Pérez Antonio
Instituto de Tecnología Química (UPV-CSIC), Universidad Politècnica de València-Consejo Superior de Investigaciones Científicas, Avda. de los Naranjos s/n, 46022, Valencia, Spain.
Commun Chem. 2024 Apr 4;7(1):76. doi: 10.1038/s42004-024-01160-z.
Metal individual atoms and few-atom clusters show extraordinary catalytic properties for a variety of organic reactions, however, their implementation in total synthesis of complex organic molecules is still to be determined. Here we show a 11-step linear synthesis of the natural product (±)-Licarin B, where individual Pd atoms (Pd) catalyze the direct aerobic oxidation of an alcohol to the carboxylic acid (steps 1 and 6), Cu clusters catalyze carbon-oxygen cross couplings (steps 3 and 8), Pd clusters catalyze a Sonogashira coupling (step 4) and Pt clusters catalyze a Markovnikov hydrosylilation of alkynes (step 5), as key reactions during the synthetic route. In addition, the new synthesis of Licarin B showcases an unexpected selective alkene hydrogenation with metal-free NaBH and an acid-catalyzed intermolecular carbonyl-olefin metathesis as the last step, to forge a trans-alkene group. These results, together, open new avenues in the use of metal individual atoms and clusters in organic synthesis, and confirm their exceptional catalytic activity in late stages during complex synthetic programmes.
金属单原子和少原子簇对多种有机反应表现出非凡的催化性能，然而，它们在复杂有机分子全合成中的应用仍有待确定。在此，我们展示了天然产物（±）-Licarin B的11步线性合成，其中单个钯原子（Pd）催化醇直接有氧氧化为羧酸（第1步和第6步），铜簇催化碳-氧交叉偶联（第3步和第8步），钯簇催化Sonogashira偶联（第4步），铂簇催化炔烃的马氏水合硅氢化反应（第5步），作为合成路线中的关键反应。此外，Licarin B的新合成展示了用无金属的硼氢化钠进行意外的选择性烯烃氢化反应，以及酸催化的分子间羰基-烯烃复分解反应作为最后一步，以形成反式烯烃基团。这些结果共同为金属单原子和簇在有机合成中的应用开辟了新途径，并证实了它们在复杂合成程序后期的卓越催化活性。
