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Molecules 2018, 23(5), 1055;

KOtBu as a Single Electron Donor? Revisiting the Halogenation of Alkanes with CBr4 and CCl4

Department of Pure and Applied Chemistry, University of Strathclyde, 295 Cathedral Street, Glasgow G1 1XL, UK
Authors to whom correspondence should be addressed.
Academic Editor: John C. Walton
Received: 8 April 2018 / Revised: 24 April 2018 / Accepted: 26 April 2018 / Published: 1 May 2018
(This article belongs to the Special Issue Radical Chemistry)
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The search for reactions where KOtBu and other tert-alkoxides might behave as single electron donors led us to explore their reactions with tetrahalomethanes, CX4, in the presence of adamantane. We recently reported the halogenation of adamantane under these conditions. These reactions appeared to mirror the analogous known reaction of NaOH with CBr4 under phase-transfer conditions, where initiation features single electron transfer from a hydroxide ion to CBr4. We now report evidence from experimental and computational studies that KOtBu and other alkoxide reagents do not go through an analogous electron transfer. Rather, the alkoxides form hypohalites upon reacting with CBr4 or CCl4, and homolytic decomposition of appropriate hypohalites initiates the halogenation of adamantane. View Full-Text
Keywords: halogenation; potassium tert-butoxide; alkanes; dihalocarbenes; hypohalite halogenation; potassium tert-butoxide; alkanes; dihalocarbenes; hypohalite

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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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Emery, K.J.; Young, A.; Arokianathar, J.N.; Tuttle, T.; Murphy, J.A. KOtBu as a Single Electron Donor? Revisiting the Halogenation of Alkanes with CBr4 and CCl4. Molecules 2018, 23, 1055.

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