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Molecules 2017, 22(4), 547; doi:10.3390/molecules22040547

Metal-Free α-C(sp3)–H Functionalized Oxidative Cyclization of Tertiary N,N-Diaryl Amino Alcohols: Theoretical Approach for Mechanistic Pathway

Gachon Institute of Pharmaceutical Science & Department of Pharmacy, College of Pharmacy, Gachon University, Yeonsu-gu, Incheon 21936, Korea
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Author to whom correspondence should be addressed.
Academic Editor: Georgiy B. Shul’pin
Received: 21 February 2017 / Revised: 18 March 2017 / Accepted: 24 March 2017 / Published: 29 March 2017
(This article belongs to the Special Issue Reactions of Hydrocarbons and other C‒H Compounds)
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Abstract

The mechanistic pathway of TEMPO/I2-mediated oxidative cyclization of N,N-diaryl amino alcohols 1 was investigated. Based on direct empirical experiments, three key intermediates (aminium radical cation 3, α-aminoalkyl radical 4, and iminium 5), four types of reactive species (radical TEMPO, cationic TEMPO, TEMPO-I, and iodo radical), and three types of pathways ((1) SET/PCET mechanism; (2) HAT/1,6-H transfer mechanism; (3) ionic mechanism) were assumed. Under the assumption, nine free energy diagrams were acquired through density functional theory calculations. From the comparison of solution-phase free energy, some possible mechanisms were excluded, and then the chosen plausible mechanisms were concretized using the more stable intermediate 7. View Full-Text
Keywords: α-C(sp3)–H functionalization; oxidative cyclization; tertiary amine; 6-exo-trig; metal-free C–H activation α-C(sp3)–H functionalization; oxidative cyclization; tertiary amine; 6-exo-trig; metal-free C–H activation
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This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. (CC BY 4.0).

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Ullah, Z.; Kim, M. Metal-Free α-C(sp3)–H Functionalized Oxidative Cyclization of Tertiary N,N-Diaryl Amino Alcohols: Theoretical Approach for Mechanistic Pathway. Molecules 2017, 22, 547.

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