Institute of Organic Chemistry & MOE Key Laboratory of Bioinorganic and Synthetic Chemistry, School of Chemistry, Sun Yat-Sen University, Guangzhou, 510275, China.
Angew Chem Int Ed Engl. 2020 Jun 26;59(27):11010-11019. doi: 10.1002/anie.202003897. Epub 2020 May 11.
An unprecedented approach for efficient synthesis of functionalized allylic gem-difluorides via catalytic fluorinative Meyer-Schuster-like rearrangement is disclosed. This transformation proceeded with readily accessible propargylic fluorides, and low-cost B-F reagents and electrophilic reagents by sulfide catalysis. A series of iodinated, brominated, and trifluoromethylthiolated allylic gem-difluorides that were difficult to access by other methods were facilely produced with a wide range of functional groups. Importantly, the obtained iodinated products could be incorporated into different drugs and natural products, and could be expediently converted into many other valuable gem-difluoroalkyl molecules as well. Mechanistic studies revealed that this reaction went through a regioselective fluorination of alkynes followed by a formal 1,3-fluorine migration under the assistance of the B-F reagents to give the desired products.
通过催化氟代 Meyer-Schuster 重排，我们发现了一种高效合成功能化烯丙基偕二氟化物的空前方法。该转化通过硫催化作用，以易得的丙炔基氟化物、低成本的 B-F 试剂和亲电试剂进行。通过其他方法难以获得的一系列碘代、溴代和三氟甲基硫代烯丙基偕二氟化物，都可以用广泛的官能团轻松地合成。重要的是，获得的碘代产物可以掺入到不同的药物和天然产物中，并且可以方便地转化为许多其他有价值的偕二氟代烷基分子。机理研究表明，该反应经历了炔烃的区域选择性氟代，然后在 B-F 试剂的辅助下，通过正规的 1,3-氟迁移，得到了所需的产物。
