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Catalytic Access to Functionalized Allylic gem ‐Difluorides via Fluorinative Meyer–Schuster‐Like Rearrangement
Author(s) -
Liao Lihao,
An Rui,
Li Huimin,
Xu Yang,
Wu JinJi,
Zhao Xiaodan
Publication year - 2020
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.202003897
Subject(s) - allylic rearrangement , chemistry , reagent , regioselectivity , catalysis , difluoride , electrophile , combinatorial chemistry , sulfide , organic chemistry , medicinal chemistry
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.