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Lewis Acid-Catalyzed Benzannulation via Unprecedented [4+2] Cycloaddition of o -Alkynyl(oxo)benzenes and Enynals with Alkynes

2003; American Chemical Society; Volume: 125; Issue: 36 Linguagem: Inglês

10.1021/ja036927r

1943-2984

Naoki Asao, Tsutomu Nogami, Sun Young Lee, Yoshinori Yamamoto,

Cyclopropane Reaction Mechanisms

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 (CH2Cl)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.