Iron-Mediated Radical Nitrohalogenation Reactions of Enynes with tert-Butyl Nitrite

Yingming Ren; Yaxin Ge; Qinqin Yan; Yunfei Tian; Jilai Wu; Yujie Yang; Lijun Li; Zejiang Li

doi:10.1055/a-1520-2192

Synlett, Table of Contents

Synlett 2021; 32(12): 1192-1196
DOI: 10.1055/a-1520-2192

letter

Iron-Mediated Radical Nitrohalogenation Reactions of Enynes with tert-Butyl Nitrite

Yingming Ren‡

^aKey Laboratory of Medicinal Chemistry and Molecular Diagnosis of the Ministry of Education, College of Chemistry and Environmental Science, Key Laboratory of Chemical Biology of Hebei Province, Hebei University, Baoding, Hebei 071002, P. R. of China

,

Yaxin Ge‡

^aKey Laboratory of Medicinal Chemistry and Molecular Diagnosis of the Ministry of Education, College of Chemistry and Environmental Science, Key Laboratory of Chemical Biology of Hebei Province, Hebei University, Baoding, Hebei 071002, P. R. of China

,

Qinqin Yan∗

^aKey Laboratory of Medicinal Chemistry and Molecular Diagnosis of the Ministry of Education, College of Chemistry and Environmental Science, Key Laboratory of Chemical Biology of Hebei Province, Hebei University, Baoding, Hebei 071002, P. R. of China

,

Yunfei Tian∗

^bCollege of Chemistry and Chemical Engineering, and Henan Key Laboratory of Function-Oriented Porous Materials, Luoyang Normal University, Luoyang, Henan 471934, P. R. of China

,

Jilai Wu

^aKey Laboratory of Medicinal Chemistry and Molecular Diagnosis of the Ministry of Education, College of Chemistry and Environmental Science, Key Laboratory of Chemical Biology of Hebei Province, Hebei University, Baoding, Hebei 071002, P. R. of China

,

Yujie Yang

^aKey Laboratory of Medicinal Chemistry and Molecular Diagnosis of the Ministry of Education, College of Chemistry and Environmental Science, Key Laboratory of Chemical Biology of Hebei Province, Hebei University, Baoding, Hebei 071002, P. R. of China

,

Lijun Li

^aKey Laboratory of Medicinal Chemistry and Molecular Diagnosis of the Ministry of Education, College of Chemistry and Environmental Science, Key Laboratory of Chemical Biology of Hebei Province, Hebei University, Baoding, Hebei 071002, P. R. of China

,

Zejiang Li ∗

^aKey Laboratory of Medicinal Chemistry and Molecular Diagnosis of the Ministry of Education, College of Chemistry and Environmental Science, Key Laboratory of Chemical Biology of Hebei Province, Hebei University, Baoding, Hebei 071002, P. R. of China

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Abstract

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Abstract

A radical nitrohalogenation/cyclization of various enynes with tert-butyl nitrite has been developed that conveniently introduces useful nitro and halo groups into organic compounds. Some control experiments were performed to elucidate the mechanism. Further functional transformations proceeded well in this reaction system.

Key words

nitrohalogenation - cyclization - enynes - butyl nitrite - radical reaction - pyrrolidines

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References

References and Notes

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17 CCDC 2056928 contains the supplementary crystallographic data for compound 1. The data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/structures
18 (4Z)-4-[Iodo(phenyl)methylene]-3-methyl-3-(nitromethyl)-1-tosylpyrrolidine; Typical Procedure A mixture of the N-tosyl(2-methylprop-2-en-1-yl)(3-phenylprop-2-yn-1-yl)amine (1 equiv, 0.1 mmol), TBN (8 equiv, 0.8 mmol), KI (1 equiv, 0.1 mmol), FeSO₄·7H₂O (0.4 equiv, 0.04 mmol), and CH₃CN (1 mL) was kept in a sealed tube at 50 °C under N₂ for 6 h. When the reaction was finished, the mixture was concentrated under a vacuum and purified by flash column chromatography [silica gel, PE–EtOAc (10:1)] to give a white solid; yield: 46.3 mg (90%; Z/E = 9:1); mp 104–105 ℃. ¹H NMR (400 MHz, CDCl₃): δ = 7.76 (d, J = 8.0 Hz, 2 H), 7.41 (d, J = 8.0 Hz, 2 H), 7.36–7.31 (m, 3 H), 7.16–7.14 (m, 2 H), 4.18 (d, J = 12.4 Hz, 1 H), 4.03 (d, J = 15.6 Hz, 1 H), 4.00 (d, J = 12.4 Hz, 1 H), 3.90 (d, J = 15.1 Hz, 1 H), 3.61 (d, J = 9.8 Hz, 1 H), 3.23 (d, J = 9.7 Hz, 1 H), 2.48 (s, 3 H), 1.10 (s, 3 H). ¹³C NMR (100 MHz, CDCl₃): δ = 144.8, 144.3, 142.1, 131.7, 130.0, 129.1, 128.7, 128.1, 127.5, 95.1, 79.7, 61.2, 59.3, 47.0, 22.5, 21.6. HRMS (ESI): m/z for [M + H]⁺ calcd for C₂₀H₂₂IN₂O₄S; 513.0339; found: 513.0338.

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