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Although a number of Lewis acids based on boron have been identified thus far, tris(pentafluorophenyl) borane [B(C6F5)3] (henceforth, BCF) has drawn the greatest interest from the synthetic chemistry community. Due to its commercial availability and thermal stability, BCF has been thoroughly investigated in organic and materials chemistry for its potential as a Lewis acid catalyst. The last two decades have witnessed the majority of BCF chemistry research in organic synthesis, and numerous novel catalytic reactivities are presently being studied. In this triennial update, which covers the period from 2021 to the present, we have thoroughly and critically reviewed the most representative applications of tris(pentafluorophenyl)borane in organic synthesis. Mechanistic studies are presented together with the scope of the catalyst.
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