Lewis acid-catalyzed benzannulation via unprecedented [4+2] cycloaddition of o-alkynyl(oxo)benzenes and enynals with alkynes

Naoki Asao, Tsutomu Nogami, Sunyoung Lee, Yoshinori Yamamoto

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    337 Citations (Scopus)

    Abstract

    The reaction of o-alkynyl(oxo)benzenes 1 with alkynes 2 in the presence of a catalytic amount of AuCl3 in (CH2Cl)2 at 80 °C gave the [4+2] benzannulation products, naphthyl ketone derivatives 3 and 4, in high yields. When the reaction was carried out using AuBr3 instead of AuCl3, the reaction speed was enhanced and the chemical yield was increased. On the other hand, when the reaction was carried out in the presence of a catalytic amount of Cu(OTf)2 and 1 equiv of a Brønsted acid, such as CF2HCO2H, in (CH 2Cl)2 at 100 °C, the decarbonylated naphthalene products 5 were obtained in high yields. Similarly, the Cu(OTf) 2-H2O-promoted reaction of the enynals 7 with an alkyne 2 afforded the corresponding [4+2] benzannulation products, decarbonylated benzene derivatives 8, in good yields. Both AuX3- and Cu(OTf) 2-catalyzed benzannulations proceed most probably through the formation of the benzo[c]pyrylium ate complex 10, the Diels-Alder addition of alkynes 2 to the ate complex, and the resulting bicyclic pyrylium ion intermediate 12. The mechanistic difference between the AuX3 and Cu(OTf)2-HA system is discussed.

    Original languageEnglish
    Pages (from-to)10921-10925
    Number of pages5
    JournalJournal of the American Chemical Society
    Volume125
    Issue number36
    DOIs
    Publication statusPublished - 2003 Sep 10

    ASJC Scopus subject areas

    • Catalysis
    • Chemistry(all)
    • Biochemistry
    • Colloid and Surface Chemistry

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