Hypervalent Iodine-Catalyzed Synthesis of 1,2,4-Oxadiazoles from Aldoximes and Nitriles

Abstract

A convenient procedure for oxidative cycloaddition of aldoximes with nitriles using stoichiometric or catalytic amounts of hypervalent iodine(III) reagent IBA-OTf (2-iodosylbenzoic acid triflate) has been developed. This efficient procedure works well for the preparation of various 1,2,4-oxadiazoles in generally high yields under mild reaction conditions. The actual oxidant in this reaction, IBA-OTf, is prepared from 2-iodosylbenzoic acid (IBA) and trifluoromethanesulfonic acid (TfOH) or it can be generated in situ from 2-iodobenzoic acid and m-chloroperoxybenzoic acid (m-CPBA) in the presence of TfOH. The nature of hydroxy(aryl)iodonium species, generated in situ from 2-iodobenzoic acid, m-CPBA, and TfOH under catalytic reaction conditions, has been confirmed by ¹H NMR spectroscopy, ESI-mass spectrometry, and by X-ray diffraction.

Original language	English
Pages (from-to)	1128-1133
Number of pages	6
Journal	Asian Journal of Organic Chemistry
Volume	5
Issue number	9
DOIs	https://doi.org/10.1002/ajoc.201600247
Publication status	Published - 1 Sep 2016

Keywords

1,2,4-oxadiazoles
cyclization
heterocycles
iodine
oxidation

ASJC Scopus subject areas

Organic Chemistry

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10.1002/ajoc.201600247

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Hypervalent Iodine-Catalyzed Synthesis of 1,2,4-Oxadiazoles from Aldoximes and Nitriles. / Yoshimura, Akira; Nguyen, Khiem C.; Klasen, Scott C.; Postnikov, Pavel S.; Yusubov, Mekhman S.; Saito, Akio; Nemykin, Victor N.; Zhdankin, Viktor V.

In: Asian Journal of Organic Chemistry, Vol. 5, No. 9, 01.09.2016, p. 1128-1133.

Research output: Contribution to journal › Article › peer-review

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abstract = "A convenient procedure for oxidative cycloaddition of aldoximes with nitriles using stoichiometric or catalytic amounts of hypervalent iodine(III) reagent IBA-OTf (2-iodosylbenzoic acid triflate) has been developed. This efficient procedure works well for the preparation of various 1,2,4-oxadiazoles in generally high yields under mild reaction conditions. The actual oxidant in this reaction, IBA-OTf, is prepared from 2-iodosylbenzoic acid (IBA) and trifluoromethanesulfonic acid (TfOH) or it can be generated in situ from 2-iodobenzoic acid and m-chloroperoxybenzoic acid (m-CPBA) in the presence of TfOH. The nature of hydroxy(aryl)iodonium species, generated in situ from 2-iodobenzoic acid, m-CPBA, and TfOH under catalytic reaction conditions, has been confirmed by 1H NMR spectroscopy, ESI-mass spectrometry, and by X-ray diffraction.",

keywords = "1,2,4-oxadiazoles, cyclization, heterocycles, iodine, oxidation",

author = "Akira Yoshimura and Nguyen, {Khiem C.} and Klasen, {Scott C.} and Postnikov, {Pavel S.} and Yusubov, {Mekhman S.} and Akio Saito and Nemykin, {Victor N.} and Zhdankin, {Viktor V.}",

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AU - Nguyen, Khiem C.

AU - Klasen, Scott C.

AU - Postnikov, Pavel S.

AU - Yusubov, Mekhman S.

AU - Saito, Akio

AU - Nemykin, Victor N.

AU - Zhdankin, Viktor V.

PY - 2016/9/1

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N2 - A convenient procedure for oxidative cycloaddition of aldoximes with nitriles using stoichiometric or catalytic amounts of hypervalent iodine(III) reagent IBA-OTf (2-iodosylbenzoic acid triflate) has been developed. This efficient procedure works well for the preparation of various 1,2,4-oxadiazoles in generally high yields under mild reaction conditions. The actual oxidant in this reaction, IBA-OTf, is prepared from 2-iodosylbenzoic acid (IBA) and trifluoromethanesulfonic acid (TfOH) or it can be generated in situ from 2-iodobenzoic acid and m-chloroperoxybenzoic acid (m-CPBA) in the presence of TfOH. The nature of hydroxy(aryl)iodonium species, generated in situ from 2-iodobenzoic acid, m-CPBA, and TfOH under catalytic reaction conditions, has been confirmed by 1H NMR spectroscopy, ESI-mass spectrometry, and by X-ray diffraction.

AB - A convenient procedure for oxidative cycloaddition of aldoximes with nitriles using stoichiometric or catalytic amounts of hypervalent iodine(III) reagent IBA-OTf (2-iodosylbenzoic acid triflate) has been developed. This efficient procedure works well for the preparation of various 1,2,4-oxadiazoles in generally high yields under mild reaction conditions. The actual oxidant in this reaction, IBA-OTf, is prepared from 2-iodosylbenzoic acid (IBA) and trifluoromethanesulfonic acid (TfOH) or it can be generated in situ from 2-iodobenzoic acid and m-chloroperoxybenzoic acid (m-CPBA) in the presence of TfOH. The nature of hydroxy(aryl)iodonium species, generated in situ from 2-iodobenzoic acid, m-CPBA, and TfOH under catalytic reaction conditions, has been confirmed by 1H NMR spectroscopy, ESI-mass spectrometry, and by X-ray diffraction.

KW - 1,2,4-oxadiazoles

KW - cyclization

KW - heterocycles

KW - iodine

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