Diverse nucleophilic carbon–electrophilic carbon σ-bonds were found to undergo facile cleavage and to add across carbon–carbon triple bonds of arynes without the aid of transition-metal catalysts, leading to the direct introduction of different carbon functionalities into the ortho-positions of aromatic rings. Active methylene compounds including β-dicarbonyl compounds, α-cyanocarbonyl compounds, sulfonylacetonitrile, and malononitrile smoothly underwent the aryne insertion reactions, and, moreover, the reaction was applicable to fluorene and trifluoromethyl ketone derivatives. The total synthesis of cytosporone B and phomopsin C, depending upon the carbon–carbon bond cleavage reaction, is also described. 1 Introduction 2 β-Dicarbonyl Compounds 3 α-Cyanocarbonyl Compounds 4 Sulfonylacetonitrile and Malononitrile 5 Fluorenes 6 Trifluoromethyl Ketones 7 Total Synthesis of Cytosporone B and Phomopsin C 8 Conclusion