Gold- and copper-catalyzed [4+2] benzannulations between enynal or enynone units and 2π-systems

被引:187
作者
Asao, Naoki [1 ]
机构
[1] Tohoku Univ, Dept Chem, Grad Sch Sci, Sendai, Miyagi 9808578, Japan
关键词
gold catalysis; copper catalysis; carbophilic Lewis acids; 4+2] benzannulation; benzo[c]pyrylium ate complexes; (+)-ochromycinone;
D O I
10.1055/s-2006-947331
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
Gold-catalyzed formal [4+2] benzannulation between enynal or enynone units, including ortho-alkynyl(oxo)benzenes, and 2 pi-systems, such as alkynes and carbonyl compounds (enol forms), produces aromatic ketones in good to high yields. By simply changing the catalyst from gold to copper-Bronsted acid system, decarbonylated aromatic compounds can be prepared in the reactions using alkynes as the 2 pi-system. An efficient synthetic approach to angucyclinone antibiotics, (+)-ochromycinone and (+)rubiginone B-2, is developed by applying the present benzannulation to an intramolecular version. The reaction proceeds most probably through the formation of the benzo[c]pyrylium ate complex via the intramolecular nucleophilic addition of the carbonyl oxygen atom to the alkyne part of enynal or enynone units, which is induced by carbophilic gold and copper catalysts.
引用
收藏
页码:1645 / 1656
页数:12
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