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A new, operationally simple approach is presented to access arynes and their fluoride-activated precursors based on Ru-catalyzed C-H silylation of arylboronates. Chromatographic purification may be deferred until after aryne capture, rendering the arylboronates de facto precursors. Access to various new arynes and their derivatives is demonstrated, including, for the first time, those based on a 2,3-carbazolyne and 2,3-fluorenyne core, which pave the way for novel derivatizations of motifs relevant to materials chemistry.

Arynes and Their Precursors from Arylboronic Acids via Catalytic C–H Silylation