Differentiation between enamines and tautomerizable imines in the oxidation reaction with TEMPO

Xiaoming Jie, Yaping Shang, Zhe-Ning Chen, Xiaofeng Zhang, Wei Zhuang () and Weiping Su ()
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Xiaoming Jie: Chinese Academy of Sciences
Yaping Shang: Chinese Academy of Sciences
Zhe-Ning Chen: Chinese Academy of Sciences
Xiaofeng Zhang: Chinese Academy of Sciences
Wei Zhuang: Chinese Academy of Sciences
Weiping Su: Chinese Academy of Sciences

Nature Communications, 2018, vol. 9, issue 1, 1-10

Abstract: Abstract Enamine and imine represent two of the most common reaction intermediates in syntheses, and the imine intermediates containing α-hydrogen often exhibit the similar reactivity to enamines due to their rapid tautomerization to enamine tautomers. Herein, we report that the minor structural difference between the enamine and the enamine tautomer derived from imine tautomerization results in the different chemo- and regioselectivity in the reaction of cyclohexanones, amines and TEMPO: the reaction of primary amines furnishes the formal oxygen 1,2-migration product, α-amino-enones, while the reaction of secondary amines under similar conditions generates exclusively arylamines via consecutive dehydrogenation on the cyclohexyl rings. The 18O-labeling experiment for α-amino-enone formation revealed that TEMPO served as oxygen transfer reagent. Experimental and computational studies of reaction mechanisms revealed that the difference in chemo- and regioselectivity could be ascribed to the flexible imine-enamine tautomerization of the imine intermediate containing an α-hydrogen.

Date: 2018
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DOI: 10.1038/s41467-018-07534-x

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