兰州大学Bing Han小组近日在有机合成研究中取得一项新成果。经过不懈努力，他们通过自由基介导的烷氧膦重排实现了未活化烯烃的区域选择性氟烷基磷酸化。该项研究成果发表在2022年5月20日出版的《德国应用化学》上。

在该研究中，课题组首次开发了一种新的烷氧膦远端自由基重排方法，并将其应用于未活化烯烃的区域选择性自由基氟烷基磷酸化反应中。利用(双)同烯基醇、氯代有机膦和氟烷基碘化物在集成荧光（CFL）照射下的一锅两步反应，课题组简易地合成了一系列氟烷基-磷酸化的烷基碘化物和醇类，这是通过在末端烯烃的内部碳原子上区域选择性地加装一个膦基以及进一步碘化/羟基化反应实现的。

机理研究表明，该迁移过程中发生了一个独特的磷原子孤对电子对的自由基环化/β-剪切，导致C-P键的形成和C-O键的断裂。

附：英文原文

Title: Regioselective Fluoroalkylphosphorylation of Unactivated Alkenes by Radical–Mediated Alkoxyphosphine Rearrangement

Author: Dong-Tai Xie, Hong-Lei Chen, Dian Wei, Bang-Yi Wei, Zheng-Hu Li, Jian-Wu Zhang, Wei Yu, Bing Han

Issue&Volume: 2022-05-20

Abstract: A novel distal radical rearrangement of alkoxyphosphine is developed for the first time and applied to the regioselective radical fluoroalkylphosphorylation of unactivated olefins. By employing a one-pot two-step reaction of (bis)homoallylic alcohols，organophosphine chlorides, and fluoroalkyl iodides under CFL (compact fluorescence light) irradiation, a series of fluoroalkyl-phosphorylated alkyl iodides and alcohols are easily synthesized by regiospecific installing a phosphonyl onto the inner carbon of terminal olefins and further iodination/hydroxylation. Mechanism studies reveal that the migration undergoes a distinctive radical cyclization/β-scission on the lone electron pair of phosphorous, resulting in the C-P bond formation and C-O bond cleavage.

DOI: 10.1002/anie.202203398

Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.202203398