Abstract
β-Nitrostyrenes underwent a Diels–Alder reaction with Danishefsky’s diene to afford cyclohexenes together with the corresponding hydrolyzed products, 3-arylated-5-methoxy-4-nitrocyclohexanones. When the reaction was conducted in the presence of water, the cyclohexenes were efficiently hydrolyzed into cyclohexanones. Subsequent aromatization by heating the cyclohexanone with a catalytic amount of iodine in dimethyl sulfoxide gave 3-arylated-4-nitrophenols. The reaction of nitrostyrenes with Danishefsky’s diene could be conducted in one pot to directly afford the corresponding nitrophenols. Moreover, a heteroaryl group, e.g., a thienyl group could be introduced into the nitrophenol framework.
Highlights
The 4-nitrophenol framework is characterized by a biased electron density in the ring and an acidic hydroxy group, which can be attributed to the electron-donating hydroxy and the electronwithdrawing nitro groups
This unique reactivity prompted us to probe the synthesis of the 3-arylated-4-nitrophenols 5 by the Diels–Alder reaction of nitrostyrenes 1 with Danishefsky’s diene (2, the trimethylsiloxy group of the diene can be converted to a phenolic hydroxy group by hydrolysis) [20], followed by the oxidation and aromatization of the obtained cyclohexanone 4 (Scheme 1)
The oxidative aromatization of 4a was achieved by the treatment with a catalytic amount of iodine in dimethyl sulfoxide (DMSO) to furnish nitrophenol 5a
Summary
Address: 1School of Environmental Science and Engineering, Kochi University of Technology, Tosayamada, Kami, Kochi 782-8502, Japan, 2Research Center for Molecular Design, Kochi University of Technology, Tosayamada, Kami, Kochi 782-8502, Japan and 3Graduate School of Pharmaceutical Sciences, Osaka University, Yamadaoka 1-6, Suita, Osaka 565-0871, Japan.
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