First synthesis of acylated nitrocyclopropanes

Kento Iwai; Rikiya Kamidate; Khimiya Wada; Haruyasu Asahara; Nagatoshi Nishiwaki

doi:10.3762/bjoc.19.67

First synthesis of acylated nitrocyclopropanes

Beilstein J Org Chem. 2023 Jun 21:19:892-900. doi: 10.3762/bjoc.19.67. eCollection 2023.

Authors

Kento Iwai^{1

2}, Rikiya Kamidate¹, Khimiya Wada¹, Haruyasu Asahara^{1

2

3}, Nagatoshi Nishiwaki^{1

2}

Affiliations

¹ School of Engineering Science, Kochi University of Technology, Tosayamada, Kami, Kochi 782-8502, Japan.
² Research Center for Molecular Design, Kochi University of Technology, Kami, Kochi 782-8502, Japan.
³ Graduate School of Pharmaceutical Sciences, Osaka University, Yamadaoka 1-6, Suita, Osaka 565-0871, Japan.

Abstract

Although nitrocyclopropanedicarboxylic acid esters are widely used in organic syntheses, nitrocyclopropanes with an acyl group have not yet been synthesized. When adducts of β-nitrostyrene and 1,3-dicarbonyl compounds are treated with (diacetoxyiodo)benzene and tetrabutylammonium iodide, iodination occurs at the α-position of the nitro group, and the subsequent O-attack of the enol moiety leads to 2,3-dihydrofuran. Cyclopropane was successfully synthesized through C-attack as the acyl group became bulkier. The obtained nitrocyclopropane was transformed into furan upon treatment with tin(II) chloride via a ring-opening/ring-closure process.

Keywords: acetoxyiodine; conjugate addition; dihydrofuran; nitroalkene; nitrocyclopropane.