Synthesis of α,β-Unsaturated N-Aryl Ketonitrones from Oximes and Diaryliodonium Salts: Observation of a Metal-Free N-Arylation Process

Xiao Pan Ma, Wei Min Shi, Xue Ling Mo, Xiao Hua Li, Liang Gui Li, Cheng Xue Pan, Bo Chen, Gui Fa Su, Dong Liang Mo

Research output: Contribution to journalArticle

34 Citations (Scopus)

Abstract

An efficient transition-metal-free method for the preparation of α,β-unsaturated N-aryl ketonitrones under mild conditions has been developed. This reaction shows good functional group tolerance for both electron-rich and electron-deficient substituents on both oximes and diaryliodonium salts. Two examples of gram-scale preparations have been realized in good yields. Further transformations of these nitrones to different N-heterocycles have been demonstrated. DFT calculations suggest that N-arylation products are formed by [1,3]-phenyl migration of an O-coordinated oximate complex via a four-centered transition state, while the O-arylation products are formed by [1,3]-phenyl migration of a N-coordinated oximate complex.

Original languageEnglish (US)
Pages (from-to)10098-10107
Number of pages10
JournalJournal of Organic Chemistry
Volume80
Issue number20
DOIs
StatePublished - Oct 16 2015

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Oximes
Salts
Metals
Electrons
Discrete Fourier transforms
Functional groups
Transition metals
nitrones

All Science Journal Classification (ASJC) codes

  • Organic Chemistry

Cite this

Ma, Xiao Pan ; Shi, Wei Min ; Mo, Xue Ling ; Li, Xiao Hua ; Li, Liang Gui ; Pan, Cheng Xue ; Chen, Bo ; Su, Gui Fa ; Mo, Dong Liang. / Synthesis of α,β-Unsaturated N-Aryl Ketonitrones from Oximes and Diaryliodonium Salts : Observation of a Metal-Free N-Arylation Process. In: Journal of Organic Chemistry. 2015 ; Vol. 80, No. 20. pp. 10098-10107.
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abstract = "An efficient transition-metal-free method for the preparation of α,β-unsaturated N-aryl ketonitrones under mild conditions has been developed. This reaction shows good functional group tolerance for both electron-rich and electron-deficient substituents on both oximes and diaryliodonium salts. Two examples of gram-scale preparations have been realized in good yields. Further transformations of these nitrones to different N-heterocycles have been demonstrated. DFT calculations suggest that N-arylation products are formed by [1,3]-phenyl migration of an O-coordinated oximate complex via a four-centered transition state, while the O-arylation products are formed by [1,3]-phenyl migration of a N-coordinated oximate complex.",
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Synthesis of α,β-Unsaturated N-Aryl Ketonitrones from Oximes and Diaryliodonium Salts : Observation of a Metal-Free N-Arylation Process. / Ma, Xiao Pan; Shi, Wei Min; Mo, Xue Ling; Li, Xiao Hua; Li, Liang Gui; Pan, Cheng Xue; Chen, Bo; Su, Gui Fa; Mo, Dong Liang.

In: Journal of Organic Chemistry, Vol. 80, No. 20, 16.10.2015, p. 10098-10107.

Research output: Contribution to journalArticle

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