One-carbon extrusion from a tetraazafulvalene. Isolation of aldehydes and a study of their origin

J.A. Murphy, F. Schoenebeck, N.J. Findlay, D.W. Thomson, S.Z. Zhou, J. Garnier

Research output: Contribution to journalArticle

27 Citations (Scopus)

Abstract

Reaction of imidazolylidene-derived enetetramine 2 with aliphatic iodides and bromides (and with aryl iodides bearing alkene-containing side-chains in the ortho-position) leads to formation of aliphatic aldehydes through an unprecedented extrusion of a one-carbon unit from the enetetramine. An intermediate 2-alkylimidazoline 24 is proposed, where the alkyl group derives from the substrate; this imidazoline undergoes further reaction in situ to afford the observed aldehydes on acidic workup. Modified substrates were designed and prepared to probe the chemistry of the alkylimidazoline adducts and provided extensive information on the chemistry of the adducts.
LanguageEnglish
Pages6475-6479
Number of pages5
JournalJournal of the American Chemical Society
Volume131
Issue number18
DOIs
Publication statusPublished - 13 May 2009

Fingerprint

Iodides
Aldehydes
Extrusion
Bearings (structural)
Carbon
Imidazolines
Alkenes
Substrates
Bromides
Olefins

Keywords

  • super electron donor
  • N-Heterocyclic carbenes
  • reductive cleavage
  • aryl iodides
  • chemistry
  • organocatalysts
  • complexes
  • salt

Cite this

Murphy, J.A. ; Schoenebeck, F. ; Findlay, N.J. ; Thomson, D.W. ; Zhou, S.Z. ; Garnier, J. / One-carbon extrusion from a tetraazafulvalene. Isolation of aldehydes and a study of their origin. In: Journal of the American Chemical Society. 2009 ; Vol. 131, No. 18. pp. 6475-6479.
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One-carbon extrusion from a tetraazafulvalene. Isolation of aldehydes and a study of their origin. / Murphy, J.A.; Schoenebeck, F.; Findlay, N.J.; Thomson, D.W.; Zhou, S.Z.; Garnier, J.

In: Journal of the American Chemical Society, Vol. 131, No. 18, 13.05.2009, p. 6475-6479.

Research output: Contribution to journalArticle

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T1 - One-carbon extrusion from a tetraazafulvalene. Isolation of aldehydes and a study of their origin

AU - Murphy, J.A.

AU - Schoenebeck, F.

AU - Findlay, N.J.

AU - Thomson, D.W.

AU - Zhou, S.Z.

AU - Garnier, J.

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AB - Reaction of imidazolylidene-derived enetetramine 2 with aliphatic iodides and bromides (and with aryl iodides bearing alkene-containing side-chains in the ortho-position) leads to formation of aliphatic aldehydes through an unprecedented extrusion of a one-carbon unit from the enetetramine. An intermediate 2-alkylimidazoline 24 is proposed, where the alkyl group derives from the substrate; this imidazoline undergoes further reaction in situ to afford the observed aldehydes on acidic workup. Modified substrates were designed and prepared to probe the chemistry of the alkylimidazoline adducts and provided extensive information on the chemistry of the adducts.

KW - super electron donor

KW - N-Heterocyclic carbenes

KW - reductive cleavage

KW - aryl iodides

KW - chemistry

KW - organocatalysts

KW - complexes

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