Aryne insertion reactions into carbon-carbon σ-bonds

摘要

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 cytosporoneB and phomopsinC, 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 CytosporoneB and PhomopsinC 8 Conclusion.