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

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 m...

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Bibliographic Details
Published inMolecules (Basel, Switzerland) Vol. 23; no. 5; p. 1055
Main Authors Emery, Katie, Young, Allan, Arokianathar, J., Tuttle, Tell, Murphy, John
Format Journal Article
LanguageEnglish
Published Basel MDPI AG 01.05.2018
MDPI
Subjects
Alkanes
Alkoxides
Carbon tetrachloride
Computer applications
Decomposition reactions
dihalocarbenes
Electron transfer
Electrons
Halogenation
hypohalite
potassium tert-butoxide
Reagents
Sodium hydroxide
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Summary: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.
ISSN:1420-3049
1420-3049
DOI:10.3390/molecules23051055