KOtBu as a single electron donor? Revisiting the halogenation of alkanes with CBr4 and CCl4

Katie J. Emery, Allan Young, J. Norman Arokianathar, Tell Tuttle, John A. Murphy

Research output: Contribution to journalArticle

Abstract

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.

LanguageEnglish
Article number1055
Number of pages16
JournalMolecules
Volume23
Issue number5
DOIs
StatePublished - 1 May 2018

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Halogenation
Adamantane
halogenation
Alkanes
alkanes
alkoxides
Electrons
electron transfer
electrons
Mirrors
hydroxides
Decomposition
reagents
mirrors
decomposition
ions

Keywords

  • alkanes
  • dihalocarbenes
  • halogenation
  • hypohalite
  • potassium tert-butoxide

Cite this

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abstract = "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.",
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KOtBu as a single electron donor? Revisiting the halogenation of alkanes with CBr4 and CCl4. / Emery, Katie J.; Young, Allan; Arokianathar, J. Norman; Tuttle, Tell; Murphy, John A.

In: Molecules, Vol. 23, No. 5, 1055, 01.05.2018.

Research output: Contribution to journalArticle

TY - JOUR

T1 - KOtBu as a single electron donor? Revisiting the halogenation of alkanes with CBr4 and CCl4

AU - Emery,Katie J.

AU - Young,Allan

AU - Arokianathar,J. Norman

AU - Tuttle,Tell

AU - Murphy,John A.

PY - 2018/5/1

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AB - 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.

KW - alkanes

KW - dihalocarbenes

KW - halogenation

KW - hypohalite

KW - potassium tert-butoxide

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