One-Carbon Extrusion from a Tetraazafulvalene. Isolation of Aldehydes and a Study of Their Origin

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 inter...

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Bibliographic Details
Published in:Journal of the American Chemical Society 2009-05, Vol.131 (18), p.6475-6479
Main Authors: Murphy, John A, Schoenebeck, Franziska, Findlay, Neil J, Thomson, Douglas W, Zhou, Sheng-ze, Garnier, Jean
Format: Article
Language:English
Subjects:
Adducts
Aldehydes
Aliphatic compounds
Extrusion
Imidazoline
Iodides
Olefins
Origins
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Summary: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.
ISSN:0002-7863
1520-5126
DOI:10.1021/ja8092746