Nagatomo Masanori, Kamimura Daigo, Matsui Yuki, Masuda Keisuke, Inoue Masayuki
Graduate School of Pharmaceutical Sciences , The University of Tokyo , Hongo, Bunkyo-ku , Tokyo 113-0033 , Japan . Email:
Chem Sci. 2015 May 1;6(5):2765-2769. doi: 10.1039/c5sc00457h. Epub 2015 Mar 6.
The single-step construction of various densely oxygenated carboskeletons was achieved by radical-based two- and three-component coupling reactions of sugar derivatives, without the need for light or heat. EtB/O-mediated decarbonylation readily converted α-alkoxyacyl tellurides to α-alkoxy carbon radicals, which intermolecularly added to glyoxylic oxime ether or enones to provide the two-component adducts. Furthermore, the three-component adducts were produced by an intermolecular aldol reaction between the aldehyde and the boron enolates generated by capture of the two-component radical intermediates by EtB. This powerful coupling method serves as a novel strategy for the convergent synthesis of polyol natural products.
通过糖衍生物基于自由基的二组分和三组分偶联反应，无需光照或加热，即可实现各种高度氧化的碳骨架的一步构建。EtB/O介导的脱羰反应可轻松将α-烷氧基酰基碲化物转化为α-烷氧基碳自由基，该自由基分子间加成到乙醛酸肟醚或烯酮上，生成二组分加合物。此外，三组分加合物是由醛与通过EtB捕获二组分自由基中间体生成的硼烯醇化物之间的分子间羟醛反应产生的。这种强大的偶联方法为多元醇天然产物的汇聚合成提供了一种新策略。
