Synlett 2020; 31(14): 1349-1360
© Georg Thieme Verlag Stuttgart · New York
Activation of C–F, Si–F, and S–F Bonds by N-Heterocyclic Carbenes and Their Isoelectronic Analogues
Ewa Pietrasiak
a
Department of Chemistry, Pohang University of Science and Technology, Pohang, 37673, South Korea
,
Eunsung Lee∗
a
Department of Chemistry, Pohang University of Science and Technology, Pohang, 37673, South Korea
b
Division of Advanced Materials Science, Pohang University of Science and Technology, Pohang 37673, South Korea Email:
eslee@postech.ac.kr
› Author Affiliations This work was supported by Korea Research Fellowship Program through the National Research Foundation of Korea (NRF, Grant No. NRF-2018R1A4A1024713) funded by the Ministry of Science and ICT (Grant No. 2019H1D3A1A01102719).
Abstract
Reactions involving C–F, Si–F, and S–F bond cleavage with N-heterocyclic carbenes and isoelectronic species are reviewed. Most examples involve activation of aromatic C–F bond via an SN Ar pathway and nucleophilic substitution of fluorine in electron-deficient olefins. The mechanism of the C–F bond activation depends on the reaction partners and the reaction can proceed via addition–elimination, oxidative addition (concerted or stepwise) or metathesis. The adducts formed upon substitution find applications in organic synthesis, as ligands and as stable radical precursors, but in most cases, their full potential remains unexplored.
1 Introduction
1.1 The C–F Bond
1.2 C–F Bond Activation: A Short Summary
1.3 C–F Bond Activation: A Special Case of SN Ar
1.4 N-Heterocyclic Carbenes (NHCs)
1.5 The Purpose of this Article
2 C–F bond Activation in Acyl Fluorides
3 Activation of Vinylic C–F Bonds
4 Activation of Aromatic C–F Bonds
5 X–F Bond Activation (X = S or Si)
6 C–F Bond Activation by Main Group Compounds Isoelectronic with NHCs
7 Conclusions and Outlook
Key words
NHC -
fluorine -
carbon–fluorine -
nucleophilic substitution -
main group elements
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