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    Cu/Pd-catalyzed borocarbonylative trifunctionalization of alkynes and allenes: synthesis of β-geminal-diboryl ketones
    (Beijing : Science China Press, 2021) Yuan, Yang; Wu, Fu-Peng; Spannenberg, Anke; Wu, Xiao-Feng
    Functionalized bisboryl compounds have recently emerged as a new class of synthetically useful building blocks in organic synthesis. Herein, we report an efficient strategy to synthesize β-geminal-diboryl ketones enabled by a Cu/Pd-catalyzed borocarbonylative trifunctionalization of readily available alkynes and allenes. This reaction promises to be a useful method for the synthesis of functionalized β-geminal-diboryl ketones with broad functional group tolerance. Mechanistic studies suggest that the reaction proceeds through borocarbonylation/hydroboration cascade of both alkynes and allenes.
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    C-F bond activation under transition-metal-free conditions
    (Beijing : Science China Press, 2021) Ai, Han-Jun; Ma, Xingxing; Song, Qiuling; Wu, Xiao-Feng
    The unique properties of fluorine-containing organic compounds make fluorine substitution attractive for the development of pharmaceuticals and various specialty materials, which have inspired the evolution of diverse C-F bond activation techniques. Although many advances have been made in functionalizations of activated C-F bonds utilizing transition metal complexes, there are fewer approaches available for nonactivated C-F bonds due to the difficulty in oxidative addition of transition metals to the inert C-F bonds. In this regard, using Lewis acid to abstract the fluoride and light/radical initiator to generate the radical intermediate have emerged as powerful tools for activating those inert C-F bonds. Meanwhile, these transition-metal-free processes are greener, economical, and for the pharmaceutical industry, without heavy metal residues. This review provides an overview of recent C-F bond activations and functionalizations under transition-metal-free conditions. The key mechanisms involved are demonstrated and discussed in detail. Finally, a brief discussion on the existing limitations of this field and our perspective are presented.