Synlett 2018; 29(11): 1465-1468
DOI: 10.1055/s-0037-1609686
letter
© Georg Thieme Verlag Stuttgart · New York

Hypervalent Iodine-Mediated Beckmann Rearrangement of Ketoximes

Ryohei Oishi
a   School of Pharmaceutical Sciences, Kindai University, 3-4-1 Kowakae, Higashi-osaka, Osaka, 577-8502, Japan   Email: y_miki@phar.kindai.ac.jp   Email: maegawa@phar.kindai.ac.jp
,
Kazutoshi Segi
a   School of Pharmaceutical Sciences, Kindai University, 3-4-1 Kowakae, Higashi-osaka, Osaka, 577-8502, Japan   Email: y_miki@phar.kindai.ac.jp   Email: maegawa@phar.kindai.ac.jp
,
Hiromi Hamamoto
b   Faculty of Agriculture, Meijo University, 1-501 Shiogamaguchi, Tempaku, Nagoya 468-8502, Japan
,
a   School of Pharmaceutical Sciences, Kindai University, 3-4-1 Kowakae, Higashi-osaka, Osaka, 577-8502, Japan   Email: y_miki@phar.kindai.ac.jp   Email: maegawa@phar.kindai.ac.jp
c   Research Organization of Science and Technology, Research Center for Drug Discovery and Pharmaceutical Science, Ritsumeikan University, 1-1-1 Nojihigashi, Kusatsu, Shiga 525-8577, Japan
,
a   School of Pharmaceutical Sciences, Kindai University, 3-4-1 Kowakae, Higashi-osaka, Osaka, 577-8502, Japan   Email: y_miki@phar.kindai.ac.jp   Email: maegawa@phar.kindai.ac.jp
,
Yasuyoshi Miki*
a   School of Pharmaceutical Sciences, Kindai University, 3-4-1 Kowakae, Higashi-osaka, Osaka, 577-8502, Japan   Email: y_miki@phar.kindai.ac.jp   Email: maegawa@phar.kindai.ac.jp
c   Research Organization of Science and Technology, Research Center for Drug Discovery and Pharmaceutical Science, Ritsumeikan University, 1-1-1 Nojihigashi, Kusatsu, Shiga 525-8577, Japan
› Author Affiliations
This work was partially supported by the MEXT-Supported Program for the Strategic Research Foundation at Private Universities, 2014-2018 (S1411037) and also by Grant-in-Aid for Young Scientists (B) (15K18840) from the Japan Society for the Promotion of Science (JSPS).

Further Information

Publication History

Received: 23 February 2018

Accepted after revision: 26 March 2018

Publication Date:
23 April 2018 (online)


Abstract

We developed a Beckmann rearrangement employing hypervalent iodine reagent under mild conditions. The reaction of ketoxime with hypervalent iodine afforded the corresponding ketone, but premixing of hypervalent iodine and a Lewis acid was effective for promoting Beckmann rearrangement. Aromatic and aliphatic ketoximes were converted into their corresponding amides in good to high yields.

Supporting Information

 
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  • 9 The experimental Procedures and Characterization Data The solution of PhI(OAc)2 (0.48 mmol) and BF3·Et2O (0.96 mmol) in CH3CN (1.0 mL) was stirred at 70 °C for 30 min. Then p-methoxyacetophenone (1a, 0.40 mmol) was added to the above mixture and stirred 70 °C for 5 min. Cooling to r.t., 0.5% aq Na2SO3 was added to the reaction mixture and extracted with CHCl3. Combined organic layer was washed with water, dried over Na2SO4, and concentrated in vacuo. The residue was purified by SiO2 column chromatography (n-hexane/AcOEt = 1:1) and preparative TLC (n-hexane/AcOEt = 5:1) to give N-(4-methoxyphenyl)acetamide (2a, 97%) as white solid. N-(4-Methoxyphenyl)acetamide (2a) White solid. 1H NMR (CDCl3): δ= 2.14 (3 H, s), 3.78 (3 H, s), 6.85 (2 H, d, J = 8.8 Hz), 7.28 (1 H, br), 7.38 (2 H, d, J = 8.8 Hz). 13C NMR (CDCl3): δ = 24.1, 55.4, 113.9, 122.0, 131.1, 156.3, 168.7.