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Alkane desaturation by concerted double hydrogen atom transfer to benzyne.

The removal of two vicinal hydrogen atoms from an alkane to produce an alkene is a challenge for synthetic chemists (1,2). In nature, desaturases and acetylenases are adept at achieving this essential oxidative functionalization reaction, for example during the biosynthesis of unsaturated fatty acid... Full description

Journal Title: Nature September 26, 2013, Vol.501(7468), pp.531-534
Main Author: Niu, Dawen
Other Authors: Willoughby, Patrick H , Woods, Brian P , Baire, Beeraiah , Hoye, Thomas R
Format: Electronic Article Electronic Article
Language: English
Subjects:
ID: E-ISSN: 1476-4687 ; DOI: 10.1038/nature12492
Link: http://search.proquest.com/docview/1437581010/?pq-origsite=primo
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recordid: proquest1437581010
title: Alkane desaturation by concerted double hydrogen atom transfer to benzyne.
format: Article
creator:
  • Niu, Dawen
  • Willoughby, Patrick H
  • Woods, Brian P
  • Baire, Beeraiah
  • Hoye, Thomas R
subjects:
  • Alkanes–Chemistry
  • Alkenes–Chemical Synthesis
  • Benzene Derivatives–Chemistry
  • Cyclization–Chemistry
  • Hydrogen–Chemistry
  • Hydrogen Bonding–Chemistry
  • Hydrogenation–Chemistry
  • Isomerism–Chemistry
  • Oxidation-Reduction–Chemistry
  • Alkanes
  • Alkenes
  • Benzene Derivatives
  • Benzyne
  • Hydrogen
ispartof: Nature, September 26, 2013, Vol.501(7468), pp.531-534
description: The removal of two vicinal hydrogen atoms from an alkane to produce an alkene is a challenge for synthetic chemists (1,2). In nature, desaturases and acetylenases are adept at achieving this essential oxidative functionalization reaction, for example during the biosynthesis of unsaturated fatty acids (3), eicosanoids, gibberellins (4) and carotenoids (5). Alkane-to-alkene conversion almost always involves one or more chemical intermediates in a multistep reaction pathway; these may be either isolable species (such as alcohols or alkyl halides) or reactive intermediates (such as carbocations, alkyl radicals, or [sigma]-alkyl-metal species). Here we report a desaturation reaction of simple, unactivated alkanes that is mechanistically unique. We show that benzynes are capable of the concerted removal of two vicinal hydrogen atoms from a hydrocarbon. The discovery of this exothermic, net redox process was enabled by the simple thermal generation of reactive benzyne intermediates through the hexadehydro-Diels-Alder cyclo-isomerization reaction of triyne substrates (6). We are not aware of any single-step, bimolecular reaction in which two hydrogen atoms are simultaneously transferred from a saturated alkane. Computational studies indicate a preferred geometry with eclipsed vicinal C-H bonds in the alkane donor.
language: eng
source:
identifier: E-ISSN: 1476-4687 ; DOI: 10.1038/nature12492
fulltext: fulltext
issn:
  • 14764687
  • 1476-4687
url: Link


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titleAlkane desaturation by concerted double hydrogen atom transfer to benzyne.
creatorNiu, Dawen ; Willoughby, Patrick H ; Woods, Brian P ; Baire, Beeraiah ; Hoye, Thomas R
contributorNiu, Dawen (correspondence author) ; Niu, Dawen (record owner)
ispartofNature, September 26, 2013, Vol.501(7468), pp.531-534
identifierE-ISSN: 1476-4687 ; DOI: 10.1038/nature12492
subjectAlkanes–Chemistry ; Alkenes–Chemical Synthesis ; Benzene Derivatives–Chemistry ; Cyclization–Chemistry ; Hydrogen–Chemistry ; Hydrogen Bonding–Chemistry ; Hydrogenation–Chemistry ; Isomerism–Chemistry ; Oxidation-Reduction–Chemistry ; Alkanes ; Alkenes ; Benzene Derivatives ; Benzyne ; Hydrogen
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descriptionThe removal of two vicinal hydrogen atoms from an alkane to produce an alkene is a challenge for synthetic chemists (1,2). In nature, desaturases and acetylenases are adept at achieving this essential oxidative functionalization reaction, for example during the biosynthesis of unsaturated fatty acids (3), eicosanoids, gibberellins (4) and carotenoids (5). Alkane-to-alkene conversion almost always involves one or more chemical intermediates in a multistep reaction pathway; these may be either isolable species (such as alcohols or alkyl halides) or reactive intermediates (such as carbocations, alkyl radicals, or [sigma]-alkyl-metal species). Here we report a desaturation reaction of simple, unactivated alkanes that is mechanistically unique. We show that benzynes are capable of the concerted removal of two vicinal hydrogen atoms from a hydrocarbon. The discovery of this exothermic, net redox process was enabled by the simple thermal generation of reactive benzyne intermediates through the hexadehydro-Diels-Alder cyclo-isomerization reaction of triyne substrates (6). We are not aware of any single-step, bimolecular reaction in which two hydrogen atoms are simultaneously transferred from a saturated alkane. Computational studies indicate a preferred geometry with eclipsed vicinal C-H bonds in the alkane donor.
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