奥地利维也纳大学Maulide, Nuno团队报道了电荷重排法实现烯烃立体发散的1,3-双官能化。相关研究成果发表在2024年1月31日出版的国际知名学术期刊《自然》。

烯烃是化学中不可缺少的原料。烯烃两个碳原子的官能化，1,2-双官能化，是世界范围内化学课程的一部分。尽管已经报道了远端位置的双官能化，但它通常依赖于具有导向基团和/或稳定特征的设计基质，所有这些都决定了键形成的最终位点。

该文中，研究人员介绍了一种基于“电荷重定位”概念的烯烃直接1,3-双官能化的方法，该方法使未活化的烯烃能够立体发散地获得顺构型或反构型的1,3-双官能团化产物，而不需要引导基团或稳定特征。该方法的有效性通过合成肺毒素4-脂肪醇及其衍生物得到了证明。

附：英文原文

Title: Stereodivergent 1,3-difunctionalization of alkenes by charge relocation

Author: Brutiu, Bogdan R., Iannelli, Giulia, Riomet, Margaux, Kaiser, Daniel, Maulide, Nuno

Issue&Volume: 2024-01-31

Abstract: Alkenes are indispensable feedstocks in chemistry. Functionalization at both carbons of the alkene—1,2-difunctionalization—is part of chemistry curricula worldwide1. Although difunctionalization at distal positions has been reported2,3,4, it typically relies on designer substrates featuring directing groups and/or stabilizing features, all of which determine the ultimate site of bond formation5,6,7. Here we introduce a method for the direct 1,3-difunctionalization of alkenes, based on a concept termed ‘charge relocation’, which enables stereodivergent access to 1,3-difunctionalized products of either syn- or anti-configuration from unactivated alkenes, without the need for directing groups or stabilizing features. The usefulness of the approach is demonstrated in the synthesis of the pulmonary toxin 4-ipomeanol and its derivatives.

DOI: 10.1038/s41586-023-06938-0

Source: https://www.nature.com/articles/s41586-023-06938-0