Institut für Anorganische Chemie, and Institute for Sustainable Chemistry & Catalysis with Boron, Julius-Maximilians-Universität Würzburg , Am Hubland, 97074 Würzburg, Germany.
Department of Organic Chemistry, Arrhenius Laboratory, Stockholm University , SE-10691 Stockholm, Sweden.
Org Lett. 2017 Mar 3;19(5):1204-1207. doi: 10.1021/acs.orglett.7b00256. Epub 2017 Feb 16.
Alcohols are among the most abundant and readily available organic feedstocks in industrial processes. The direct catalytic functionalization of sp C-O bonds of alcohols remains the main challenge in this field. Here, we report a copper-catalyzed synthesis of benzyl-, allyl-, and allenyl-boronates from benzylic, allylic, and propargylic alcohols, respectively. This protocol exhibits a broad reaction scope (40 examples) and high efficiency (up to 95% yield) under mild conditions, including for the preparation of secondary allylic boronates. Preliminarily mechanistic studies suggest that nucleophilic substitution is involved in this reaction.
醇类是工业过程中最丰富和最易得的有机原料之一。醇类中 sp³ C-O 键的直接催化官能团化仍然是该领域的主要挑战。在这里，我们报道了一种铜催化的从苄基、烯丙基和炔丙醇分别合成苄基、烯丙基和烯丙基硼酸酯的方法。该方案在温和条件下具有广泛的反应范围（40 个实例）和高效率（高达 95%的产率），包括用于制备仲烯丙基硼酸酯。初步的机理研究表明，该反应涉及亲核取代。
