An Organometallic Route to 2′-Hydroxy-6′-methoxy-acetophenone

Abstract 2′-Hydroxy-6′-methoxyacetophenone was obtained in 66% yield from 3-methoxyphenol. In the key step, 3-methoxyphenol protected by means of ethylvinyl ether was selectively metallated at the 2-position with butyllithium. Addition of ZnCl2 to the aryllithium gave the corresponding organozinc compound, which readily reacted on acetyl chloride under palladium catalysis.

[1]  G. Cahiez,et al.  Organomanganese (II) reagents XXIII: Manganese-catalyzed acylation of organomagnesium compounds by car☐ylic acid chlorides , 1992 .

[2]  L. Pieters,et al.  4'-Hydroxy-3-methoxyflavones with potent antipicornavirus activity. , 1991, Journal of medicinal chemistry.

[3]  G. Bringmann,et al.  Chiral building blocks for the synthesis of nitrogen‐containing natural products, 5. The enantioselective synthesis of optically active, benzene nucleus‐substituted 1‐phenylethylamines from the corresponding acetophenones , 1990 .

[4]  T. L. Gilchrist,et al.  Synthesis of 3-substituted furans by directed lithiation and palladium catalysed coupling , 1990 .

[5]  Hiroshi Takahashi,et al.  Heterocycles. XX. : Reactions of 2"-Methoxymethoxychalcone Epoxides under Acidic Conditions , 1986 .

[6]  R. Grey.  A palladium-catalyzed synthesis of ketones from acid chlorides and organozinc compounds , 1984 .

[7]  J. Normant,et al.  Reactivite des derives organomanganeux—VIII : Préparation de cétones par acylation d'organomanganeux. Influence de la nature de l'agent acylant, des solvants et des ligands☆ , 1984 .

[8]  E. Negishi,et al.  Palladium-catalyzed acylation of organozincs and other organometallics as a convenient route to ketones☆ , 1983 .

[9]  B. Chenard,et al.  Organocopper chemistry of quinone bisketals. Application to the synthesis of isoprenoid quinone systems , 1980 .

[10]  B. C. Ream,et al.  Preparation of benzylpalladium(II) derivatives and their reactions with metal acetates in acetic acid , 1969 .

[11]  K. Wallenfels.  Synthese von 2-Äthyl-3.5.6 (oder 7).8-tetraoxy-naphthochinon-(1.4). , 1942 .

[12]  W. Baker.  204. The synthesis of 5 : 6-dihydroxyflavone and the structure of primetin , 1939 .

[13]  W. Baker.  429. Attempts to synthesise 5 : 6-dihydroxyflavone (primetin) , 1934 .